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Corrosion Resistance of

Nickel-Containing Alloys
in Organic Acids
and Related Compounds

Table of Contents
PART I.

INTRODUCTION
A. The Organic Acids
4
B. Scope
4
C. Corrosion Testing in Organic Acid Media
4
PART II. ACETIC ACID
A. General
5
B. Austenitic Stainless Steels
5
1. General
5
2. Effect of Alloy Composition
6
3. Effect of Contaminants
10
4. Effect of Temperature
12
5. Effect of Microstructure
14
6. Quality Control
15
C. Martensitic & Ferritic Stainless Steels
15
D. Duplex Austenitic-Ferritic and Precipitation
Hardening Stainless Steels
15
E. Iron-Base Nickel-Chromium-Copper
Molybdenum Alloys
16
F. Nickel-Base Chromium-Iron-MolybdenumCopper Alloys
17
G. Iron-Base Nickel-Chromium-Molybdenum Alloys18
H. Nickel-Base Molybdenum-Chromium-Iron Alloys 18
I.
Nickel-Copper Alloys
20
J. Copper-Nickel Alloys
21
K. Nickel-Chromium Alloys
23
L. Iron-Nickel-Chromium Alloys
23
M. Nickel-Base Molybdenum Alloys
24
N. Nickel
24
O. Process and Plant Corrosion Data
25
l. Acetic Acid Production
25
a. Oxidation of Acetaldehyde
25
b. Liquid Phase Oxidation of
Straight-Chain Hydrocarbons
26
c. Methanol-Carbon Monoxide Synthesis
28
2. Acetic Acid Storage and Shipping
28
3. Vinegar Production and Storage
29
P. Acetic Anhydride
29
PART III. OTHER ORGANIC ACIDS
A. Formic Acid
31
B. Acrylic Acid
36
C. C3 Through C8 Acids
38
(Propionic, Butyric and Higher Acids)
D. Fatty Acids
44
(Lauric, Oleic, Linoleic, Stearic, Tall Oil Acids)
E. Di and Tricarboxylic Acids
46
(Oxalic, Maleic, Phthalic, Terephthalic,
Adipic, Glutaric and Pimelic Acids)
F. Naphthenic Acids
52
G. Organic Acids with Other Functional Groups
53
1. Glycolic Acid
53
2. Lactic Acid
53
3. Tartaric Acid
54
4. Citric Acid
54
5. Chloroacetic Acids
56
6. Amino Acids
57
7. Sulfoacetic Acid
57
PART IV ESTER PREPARATIONS
A. Acetic Esters
58
B. Phthalate Esters
60
C. Esterification of Fatty Acids
60
D. Acrylate Esters
60
References
Trademarks

Page 1

64
Inside Back Cover

Nominal Composition of Nickel-Containing Alloys in Use or Corrosion Tested


in Organic Acids and Related Compounds
Composition, %
Alloys

Ni

Fe

Cr

Mo

Cu

Si

Mn

Other

WROUGHT ALLOYS
Stainless SteelsAustenitic
AISI Type 201
AISI Type 202
AISI Type 204
AISI Type 204L
AISI Type 216
AISI Type 216L
AISI Type 304
AISI Type 304L
AISI Type 309
AISI Type 310
AISI Type 316
AISI Type 316L
AISI Type 317
AISI Type 317L
AISI Type 318
AISI Type 321
AISI Type 330
AISI Type 347

4.5
5.0
5.0
6.0
6.0
6.0
9.5
10.0
13.5
20.0
13.0
13.0
14.0
14.0
14.0
11.0
35.0
11.0

Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance
Balance

17.0
18.0
18.0
18.0
19.5
19.5
18.5
18.5
23.0
25.0
17.0
17.0
19.0
19.0
18.0
18.0
15.0
18.0

2.25
2.25
3.25
3.25
3.25

NITRONIC alloy 50

12.5

Balance

22.0

6.5
4.5
4.0
7.0
7.0

Balance
Balance
Balance
Balance
Balance
Balance

29.0
34.0

Stainless SteelsDuplex and


Precipitation Hardening
AISI Type 326
AISI Type 329
CRUCIBLE alloy 223
17-4PH
17-7PH
PH15-7Mo
Iron-Base Nickel-Chromium
Copper-Molybdenum Alloys
CARPENTER alloy 20(1)
CARPENTER alloy 20Cb-3

0.15 Max
0.15 Max
0.08 Max
0.03 Max
0.08 Max
0.03 Max
0.08 Max
0.03 Max
0.20 Max
0.25 Max
0.08 Max
0.03 Max
0.08 Max
0.03 Max
0.08 Max
0.08 Max
0.25 Max
0.08 Max

1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max

6.5
8.0
8.0
8.0
8.0
8.0
1.5
1.3
2.0 Max
2.0 Max
1.7
1.8
2.0 Max
2.0 Max
2.5 Max
2.0 Max
2.0 Max
2.0 Max

N 0.25 Max
N 0.25 Max
N 0.25 Max
N 0.25 Max
N 0.25-0.50
N 0.25-0.50

1.53.0

0.06 Max

1.0 Max

5.0

N 0.2-0.4, Cb 0.1-0.3

26.0
27.5
16.0
16.5
17.0
15.0

1.02.0
0.4

2.5

1.0
4.0

0.06 Max
0.10 Max
0.03 Max
0.07 Max
0.09 Max
0.09 Max

0.40
1.0 Max
1.0 Max
1.0 Max
1.0 Max
1.0 Max

0.40
2.0 Max
12.0
1.0 Max
1.0 Max
1.0 Max

N 0.3
Cb + Ta 0.3
Al 1.1
Al 1.1

43.0

20.0

2.0 Min

3.0 Min

0.07 Max

1.0

0.8

39.0

20.0

2.5

3.3

0.07 Max

0.6

0.8

Cb + Ta 0.6

0.03
0.03

0.35
0.35

0.65
1.3

AI 0.15, Ti 0.9
W 0.5. Cb + Ta 2.12

Cb + Ta 10XC Min
Ti 5XC Min
Cb + Ta 10XC Min

Nickel-Base Chromium-Iron
Molybdenum-Copper Alloys
INCOLOY alloy 825
HASTELLOY alloy G
Iron-Base Nickel-Chromium
Molybdenum Alloys
ALLEGHENY alloy AL-6X
HAYNES alloy 20 Mod
JESSOP alloy JS-700
MULTIMET alloy

41.8
45.0

30.0
19.5

21.5
22.2

3.0
6.5

1.8
2.0

24.0
26.0
25.0
20.0

46.0
42.0
46.0
29.0

20.0
22.0
21.0
21.0

6.5
5.0
4.5
3.0

0.025 Max
0.05 Max
0.03
0.12

0.5 Max
1.0 Max
0.5
1.0 Max

1.5 Max
2.5 Max
1.7
1.5

Nickel-Base Molybdenum
Chromium-Iron Alloys
HASTELLOY alloy C(2)
HASTELLOY alloy C-276
HASTELLOY alloy C-4
HASTELLOY alloy N
INCONEL alloy 625

54.0
54.0
61 ..0
69.0
60.0

5.0
5.0
3.0 Max
5.0
5.0 Max

15.5
15.5
16.0
7.0
21.5

16.0
16.0
15.5
16.5
9.0

0.08 Max
0.02 Max
0.015 Max
0.06
0.1 Max

1.0 Max
0.05 Max
0.08 Max
0.3
0.5 Max

1.0 Max
1.0 Max
1.0 Max
0.3
0.5 Max

Co2.5Max,W4.0, V 0.4 Ma)


Co2.5Max,W4.0, V 0.4 Ma)
Co 2.0 Max, Ti 0.7 Max
AI 0.5
Cb + Ta 3.65

Nickel-Copper Alloys
MONEL alloy 4OO
MONEL alloy K-500

66.0
65.0

1.35
1.0

31.5
29.5

0.12
0.15

0.15
0.15

0.9
0.6

AI 2.8, Ti 0.5

10.0
20.0
30.0

1.25
0.75
0.55

88.0
78.0
67.0

76.0
80.0

7.2

15.8
20.0

0.1

0.04

Ti 4XC Min
Cb 0.30
Co 20.0, W 2.5, N
0.15,Cb + Ta1.0

Copper-Nickel Alloys
Copper-Nickel alloy C70600
Copper-Nickel alloy C71000
Copper-Nickel alloy C71500

0.3
0.4
0.5

Nickel-Chromium Alloys
INCONEL alloy 600
NICHROME V

Page 2

0.2

0.2

Pb 0.05 Max, Zn 1.0 Max


Pb 0.05 Max, Zn 1.0 Max
Pb 0.05 Max, Zn 1.0 Max

Nominal Composition of Nickel-Containing Alloys in Use or Corrosion Tested


in Organic Acids and Related Compounds
Composition, %

Alloys

Ni

Fe

Cr

Mo

Cu

Si

Mn

Other

Iron-Nickel-Chromium Alloys
INCOLOV alloy 800
INCOLOY alloy 804

32.0
41.0

46.0
25.4

20.5
29.5

0.3
0.25

0.04
0.05

0.35
0,38

0.75
0,75

Nickel-Base Molybdenum Alloys


HASTELLOY alloy B*

61.0

5.0

1.0 Max

28.0

0.05 Max 1.0 Max

67.0

2.0 Max 1.0 Max

28.0

0.02 Max 0.1 Max

68.0
35.0
15.0
10.0

7.0

15.0
3.0 Max

15.0
20,0
20A
20.0

3.0
10.0
7.0

0.06

0.15
0.10

1.0 Max

2.0
1.5

Stainless Steels
ACI CD-4MCu
ACI CF-3
ACI CF-3M
ACI CF-8
ACI CF-8M
ACI CG-8M
ACI HK

5.5
10.0
11.0
9.0
10.0
11.0
20.0

61.0
66.0
63.0
67.0
64.0
62.0
49.0

26.0
19.0
19.0
19.0
19.0
19.0
26.0

2.0

2.5

2.5
3.5

3.0

0.04 Max
0.03 Max
0.03 Max
0.08 Max
0.08 Max
0.08 Max
0.4

1.0 Max
2.0 Max
1.5 Max
2.0 Max
2.0 Max
1.5 Max
2.0 Max

1.0 Max
1.5 Max
1.5 Max
1.5 Max
1.5 Max
1.5 Max
2.0 Max

Iron-Base Nickel-ChromiumCopper-Molybdenum Alloys


ACI CN-7M3)
WORTHITE

29.0
24.0

44.0
48.0

20.0
20.0

1.0
3.3

1.5 Max
0.6

8.0

58.0

28.0

2.0

3.0

0.75

0.75

24.0
20.0

44.0
50.0

21.0
16.0

5.0
2.0

5.0

57.0

26.0

2.0

0.5 Max

0.08

1.0 Max

58.0

5.0

22.0

6.0

6.0

0.2

0.2

58.0
57.0

6.0
3.0 Max

16.5
18.5

17.0
18.5

0.12 Max 1.0 Max


0.07 Max 1.0 Max

1.0 Max
1.0 Max

60.0
62.0

5.0
1.0 Max
3.0 Max 1.0 Max

28.0
31.5

0.12 Max 1.0 Max


0.07 Max 1.0 Max

1.0 Max V 0.20.6, Co 2.5 Max


1.0 Max

80.0
75.0
70.0
55.0
49.0
3.0 Max

0.4
5.0
1.0
3.0
3.0 Max

12.5
28.0
28.0
31.0

3.0
8.0
8.0

5.0
5.0

STELLITE alloy No. 4


STELLITE alloy No. 6

3.0 Max
3.0 Max

3.0 Max
3.0 Max

30.0
29.0

1.5 Max
1.5 Max

Nickel Alloyed Cast Irons


Ni-Resist Type 2
Ni-Resist Type 4

20.0
30.5

70.0
55.0

2.2
5.0

WROUGHT ALLOYS

HASTELLOY alloy B-2


Other Nickel and Cobalt-Base
Alloys
IN-102
MP-35N
ELGILOY
HAYNES alloy No. 25

AI 0.3, Ti 0.6

1.0 Max Co 2.5 Max, V 0.3,


P 0.025 Max, S 0.03 Max
1.0 Max Co 1.0 Max, P 0.04 Max, S
0.03 Max

Ti 0.5, Cb 2.9. A1 0.5, W 3.0


Co 35.0
Co 40.0, Be 0.05
Co. 49.0, W 15.0

CAST ALLOYS

Iron-Base Chromium-NickelCopper-Molybdenum Alloy


ILLIUM alloy P
Iron-Base Nickel-ChromiumMolybdenum Alloys
IN-862
KROMARC 55
Iron-Base Chromium-NickelIron Alloy
ILLIUM alloy PD
Nickel-Base ChromiumMolybdenum-Copper-Iron Alloy
ILLIUM alloy G

2.0 Min 3.0 Min 0.07 Max


3.0
1.75 0.07 Max

0.20

0.07 Max
0.8
0.04
2.0 Max

0.5
9.5

1.0 Max Co 7.0

1.25 Max

Nickel-Base MolybdenumChromium-Iron Alloys


ACI CW-12M-1(4)
ACI CW-12M-2(5)
Nickel-Base Molybdenum Alloys
ACI N-12M-1(6)
ACI N-12M-2(7)
Other Nickel and Cobalt-Base
Alloys
WAUKESHA alloy 23
WAUKESHA alloy 54
WAUKESHA alloy 88
ILLIUM alloy 98
ILLIUM alloy B
(8)
STELLITE alloy No. 3
(8)

(1)
(2)
(3)
(4)

An improved version of this alloy, CARPENTER alloy 20 Cb-3, has replaced


CARPENTER alloy 20.
Improved versions of this alloy, HASTELLOY alloys C-276 or C-4, have
replaced HASTELLO alloy C.
Cast type20 alloys such as DURIMET alloy 20, ALOYCO alloy 20, etc.
Includes alloys such as cast HASTELLOY alloy C, ALOYCO alloy N-3,
ILLIUM alloy W1, etc.

Sn 8.0, Zn 7.5, Pb 4.0

2.5
Sn 8.0, Zn 7.0, Ag 6.0
0.05 Max

Sn 4.0, Bi 3.75
0.05
0.7 Max 1.25 Max
0.05
4.5
1.25 Max B 0.05-0.55
2.35
1.0 Max 1.0 Max W 12.5, Others 1.0 Max,
Bal Co
1.0 Max 1.5 Max 1.0 Max W 14.0, Bal Co
1.1
1.5 Max 1.0 Max W 4.5, Bal Co

0.5 Max 3.0 Max


0.5 Max 2.6 Max

1.9
5.5

1.2
0.6

(5) Includes alloys such as CHLORIMET alloy 3, ILLIUM alloy W2, etc.
(6) Includes alloys such as cast HASTELLOY alloy B, ILLIUM alloy M1,etc.
(7) Includes alloys such as CHLORIMET alloy 2, ILLIUM alloy M2, etc.
(8) STELLITE alloys 3 and 4 are cast wear resistant alloys that are no longer
produced by Cabot Corporation.
* An improved version of this alloy, HASTELLOY alloy B-2 has
replaced HASTELLOY B.

Page 3

PART I. INTRODUCTION

B. Scope

A. The Organic Acids


The organic acids constitute a group of the most important
reactive chemicals of industry today. Billions of pounds of
acetic acid are produced in the United States every year to
provide the precursor for numerous products from aspirin to
the recovery of zaratite minerals. Acetic acid is best known
as the astringent compound in vinegar, but the acid and its
anhydride are used in the manufacture of cellulosic fibers,
commercial plastics, agricultural chemicals, dyes, plasticizers, certain explosives, ester solvents, metal salts;
pharmaceuticals such as aspirin, sulfa drugs, vitamins, and
as a precursor for a host of other organic compounds used in
the preparation of drugs.
Other organic acids are produced in much smaller
volume, but constitute important chemicals for the preparation of compounds used daily in our lives. The reactive acid
(carboxyl) group present in these organic molecules is
responsible for their wide use as ready building blocks for
many commercial compounds.
Research efforts to provide these chemicals in greater
quantity at less cost has paralleled their increasing importance. A multitude of processes have been commercialized
for the production of acetic, acrylic, adipic, lactic and the
higher acids. The volume and use of corrosive by-product
formic acid has continually increased. In all of these
processes, nickel-containing alloys are standard materials of
construction to withstand the corrosive environment and
maintain product purity.

This bulletin attempts to characterize the corrosion resistance of alloys in the wide range of exposure conditions
employed today in the production and handling of the
organic acids. Space does not allow the complete coverage
of alloy use in all organic acid processes, or even full
treatment of such a large subject as acetic acid production.
However, once the basic properties of the alloys in such
media are established, along with adequate warning of
problems to be avoided, the judicious choice of an alloy for
a similar application can usually be made. The major pitfall
in such use of data is assurance that the recorded conditions
of exposure are indeed the same as those existing in the
proposed application. Only parts per million of certain
contaminants in an organic acid process stream can have a
profound effect on the corrosion rate of an alloy. Thus, it is
critical to learn the details of proposed operating conditions,
as well as the possibilities for inadvertent changes in stream
composition.
Corrosion data reported throughout this bulletin must be
interpreted as providing valuable information regarding the
relative corrosion resistance of the various alloys in specific
environments and modes of testing. Retesting of the alloys,
particularly those containing chromium, under the same
apparent conditions may provide variations in corrosion
rates of two to three times. However. the relative resistance
of the various alloys normally remains the same.
Corrosion data for alloys in all of the many organic acids
are reported when they are available. Extensive data for the
more common acids encountered are reported. In addition,
data for representative homologues of the various types of
organic acids are reported. With this information as a guide,
the interested party should be able to select candidate
materials for an organic acid exposure of any type.
The nominal composition of alloys cited in the tables and
text are shown in the table on pages 2 and 3. An attempt has
been made to provide as comprehensive a listing of alloys as
possible to achieve the maximum utility from these data.
Some of the proprietary alloys have been improved by
compositional modifications. Where data exist for the newer
modification they are included; however, some data on the
obsolete alloys are included. Corrosion rates on the newer,
improved alloys may be assumed to be approximately
equivalent. Trademarks of proprietary alloys have been used
in the text and are listed on the inside back cover. All
materials are assumed to be in the mill annealed condition
unless notations to the contrary are shown.

C. Corrosion Testing in Organic Acid Media

Type 316L stainless steel tanks and piping and cast ACI CF-8M pumps
and valves are utilized in this plant handling organic acids. Courtesy
Walworth Company-Aloyco Valves.

Page 4

Some of the techniques used for determining corrosion rates


and changes in environment in aqueous systems are difficult
to apply in organic acid media. The specific conductance of the higher acid concentrations is low for electrochemical studies and the low dissociation constant of the
common organic acids requires major dilution of the compounds before reliable electrochemical data can be obtained.

Attempts to make potentiometric measurements are most


successful in the dilute solutions; ten per cent acetic acid is
often used as an investigative medium. Also, the addition of
sodium salts or chloride salts is reported to allow measure1
ment of potential changes with current variations. However, many electrochemical investigators have reported data
obtained in strong acetic acid, acetic acid-anhydride and
formic acid solutions. These tests showed an active-passive
behavior for most alloys, which is consistent with field
experience.
The influence of even tenths of a per cent of water in an
organic acid can have considerable influence on corrosion.
Anomalous results obtained in glacial acetic acid are
often attributable to small differences in water content in the
two different media. In any event, proper testing of alloys in
anhydrous organic acid environments is restricted to gravimetric techniques, mechanical measurements or by the use
of changes in electrical resistance of metal cross sections as
corrosion occurs.
Data are often obtained by immersion testing in the
laboratory. Such tests must be assumed to be without
control of the atmosphere unless aeration, nitrogen sparging, or other gaseous injections are identified. Without
control of the atmosphere, a test environment above
ambient temperature will have two periods of differing
exposures. Initially the solution will be air-saturated, while

in the second period little if any air will be present in boiling


solutions and a loss of oxygen will occur in solutions held at
the lower temperatures. Thus, short test periods can provide
results totally different from those obtained by longer
exposure times. Unless specifically stated to the contrary in
the tests reported, it must be assumed that air was present, at
least initially, in a laboratory test and was probably absent in
a field test.
In addition, corrosion products form in the test medium
and can exert a controlling influence on the corrosion rates
in long-term laboratory tests. Aggressive, highly-ionic
media, such as the mineral acids, may attack a metal surface
almost immediately on contact, and even on those metals
and alloys having protective oxide films the passive period
may be very short. However, when evaluating materials in
acids such as acetic, a considerable variation in rate of
corrosion can be obtained depending on the length of the
test period and the incubation period required to initiate
corrosion. With these and other factors operative, it is not
surprising that considerable discrepancy in corrosion data
exists for the exposure of alloys in organic acids.
All percentages expressed in the data are in weight per
cent unless another basis is specifically stated. Corrosion
rates are reported in millimeters per year (mm/y) followed
by the corrosion rate in mils per year (mpy) (one mil =
0.001 inch.)

PART II. ACETIC ACID

A. General
Acetic acid and its derivatives are produced in large quantities as commercial products. Perhaps of even greater
interest from a corrosion standpoint is the fact that in
industries processing many other organic chemicals, acetic
acid is a common impurity in process streams as a result of
the oxidation of lower compounds or the degradation of
larger molecules. Consequently, a knowledge of the corrosive potential of the acid is necessary to assure the
economic life of equipment or to prevent contamination of
process streams with metallic corrosion products.
Although acetic acid has a low ionization constant compared with many other acids, the effective acidity of
aqueous streams contaminated with the acid increases
rapidly with concentration. Table I shows change of pH
with concentration of acetic acid.
A wide range of alloys can be used in acetic acid
exposures. Those alloys renowned for resistance to oxidizing conditions are often a first choice for a specific exposure
while in a remarkably similar application the wisest choice
will be alloys used to combat reducing conditions. In some
process areas, both can be equally resistant and an economic
comparison is necessary before making a choice. However,
a thorough appraisal of each exposure must be made to
identify the optimum material of construction.

Page 5

B. Austenitic Stainless Steels


1. General
The wrought and cast austenitic stainless steels serve as the
workhorse of industries handling acetic acid. The addition
of sufficient nickel to iron-base alloys containing chromium
is necessary to provide the optimum alloy for ease of
fabrication and adequate resistance to attack by the acid.
In a typical acetic acid production facility, such as exemplified by the direct oxidation of hydrocarbons to the acid, the
reactors, distillation columns, heat exchangers, separators,
decanters and much of the tankage are constructed of
TABLE I
Concentration of Acetic Acid Versus
pH in Aqueous Solution
Concentration
g/I

pH

0.0006
0.006
0.06
0.6
6.0
60.0 (6%)

5.2
4.4
3.9
3.4
2.7
2.4

Reference 43

Cast ACI CF-8M valves and pumps in finished acetic acid storage
service. Piping and tanks are constructed of Type 316L stainless steel.
Courtesy Walworth Company-Aloyco Valves.

In the vast majority of exposures, there is no difference in


corrosion resistance between the wrought and cast alloys of
similar analysis provided that both are in proper metallurgical condition (annealed). The presence of small amounts of
delta ferrite (2-10%) normally found in the austenitic matrix
of the cast alloys does not lessen the corrosion resistance of
the metal as illustrated by Table II. Even greater amounts of
ferrite will show no deleterious effects in most pure acid
2
media. Flowers, et al. investigated ferrite contents in the
CF-8 and CF-BM alloys up to 38 per cent and claim anodic
polarization of the ferrite in such a dual phase alloy reduces
overall attack on the metal. However, such passivity is not
to be expected under all conditions of organic acid exposure
and thorough testing of specific alloy compositions is
advised.
Other comparative data for the cast alloys may be found
in Table XXVII and Figure 1.
2. Effect of Alloy Composition

wrought Type 316 stainless steel, or Type 316L stainless


steel if weld fabrication is to be employed. Forgings of
these alloys are found as valve parts, perhaps as heat
exchanger tube sheets, and for certain other structural parts.
The pumps and many valves are constructed of the cast
counterpart of the Type 316L stainless steel analysis known
as ACI CF-3M. The ACI CF-8M (0.08 max carbon) is
equally acceptable if in the solution annealed condition but
has the disadvantage that weld repairs have to be followed
by solution annealing to restore corrosion resistance.

The addition of proper chromium-nickel ratios in a ferrous


base to provide an austenitic stainless steel affords a limited
resistance to organic acid exposures. Lower concentrations
of pure acetic acid may be handled to the boiling point or
the higher concentrations may be used to some 90 C (194 F)
with Fe-Cr-Ni alloys such as Type 304 stainless steel.
Adding greater amounts of chromium and nickel (Types
309 and 310 stainless steels) does not change the corrosion
resistance of the alloys basically (see Table III). Using
graphical multiple correlation techniques, Dillon has shown
that chromium and nickel variations of the commercial
3
alloys have little effect on the resistance to acetic acid.
At this time, there is no reason to believe that obtaining
an austenitic matrix by the use of combinations of nickel,
manganese and nitrogen imparts any change in the organic
4
acid resistance of the alloy. That is, a Type 204 stainless
steel is equivalent to a Type 304 stainless steel and Type
216 is as resistant to acid attack as Type 316. See data in
Tables III through V for the corrosion of the high
manganese and nitrogen-containing stainless steels.

FIG 2 Effect of Molybdenum Content on Corrosion of Austenitic


Stainless Steels in Condensate from Boiling Acetic Acid
Solutions

FIG 1 Corrosion of Cast Stainless Steels in Glacial Acetic Acid

Page 6

TABLE II
Comparison of Cast Stainless Steels with Wrought
Type 316 Stainless Steel in Organic Acid Media
Test Conditions: All tests at boiling temperature for approximately 150 hours in laboratory.
Each result shown represents duplicate specimens.
Corrosion Rate
ACI CF-8M
Annealed
Temperature
Solution
Glacial Acetic Acid
50% Acetic Acid
10% Acetic Acid
85% Acetic-15% Formic
50% Acetic-15% Formic
85% Formic-15% Acetic
88% Formic Acid
50% Formic Acid
10% Formic Acid

5%*

Sensitized

10%*

5%*

mm/y mpy

mm/y mpy mm/y

117
102
100.5
109
106.5
104.5
104.5
102
100

242
216
213
228
224
220
220
216
212

.05
.03
<.03
.15
.30
.84
48
.64
.38

.05
.03
<.03
.18
33
.89
43
76
36

2
1
<1
6
12
33
19
25
15

2
1
<1
7
13
35
17
30
14

.03
.03
.03
.13
.18
.23
.28
.61
.46

10%*

Wrought
Type 316
Stainless
Steel
Annealed

mpy mm/y mpy mm/y


1
1
1
5
7
9
11
24
18

.03
03
01
.15
.20
.25
.28
.66
.46

1
1
0.5
6
8
10
11
26
18

.05
Nil
Nil
.08
.25
.13
.33
.51
.43

CD-4MCu

mpy mm/y
2
Nil
Nil
3
10
5
13
20
17

Type 329
Stainless
Steel

ACI

Nil
Nil
Nil
<.03
08
15
18
.15
<.03

WORTHITE**

mpy mm/y
Nil
Nil
Nil
<1
3
6
7
6
<1

ALLOYCO
20***

mpy mm/y mpy

03
Nil
Nil
<.03
<.03
03
05
.15
08

1
Nil
Nil
<1
<1
1
2
6
3

<.03
.03
<.03
<.03
<.03
.03
.03
.10
.10

<1
1
<1
<1
<1
1
1
4
4

mm/y

mpy

<.03
<.03

.64
1.35
1.65
8.38

<1
<1

25
53
65
330

*% Ferrite in alloy
**Trademark of Worthington Corp.
***Trademark of Aloyco, Inc.

TABLE III
Field Tests in Acetic Acid Distillation Columns
Location in Column
Test Duration (Days)
Temperature C (F)
Per Cent Acetic Acid
Alloy
Type 316 stainless steel
Type 304 stainless steel
Type 309 stainless steel
Type 329 stainless steel
Type 216 stainless steel
Type 410 stainless steel
Type 430 stainless steel
1
CARPENTER alloy 20Cb-3
2
JESSOP alloy JS-700
3
INCOLOY alloy 825
4
HASTELLOY alloy C*
5
CHLORIMET alloy 2
HASTELLOY alloy B
3
INCONEL alloy 600
3
MONEL alloy 400
C 10300 (Copper)
Nickel 200

Top
11
120 (248)
99.5+
mm/y
<.03
.30
.89
.03
<.03

Top
40
106 (223)
99.9+

mpy
<1
12
35
1
<1

mm/y
< .03

Mid
375
100 (212)
20

mpy
<1

>12.7
>12.7
<.03

.15
.08
.15
.08

6
3
6
3

<1
<1

.08

Corrosion Rate
mm/y
mpy
.05
2

>500
>500
<1

<.03
<.03

Bottom
62
121 (250)
99.9+

(1) Trademark of Carpenter Technology Corporation


(2) Trademark of Jessop Steel Company
(3) Trademark of the Inco family of companies
(4) Trademark of Cabot Corporation
(5) Trademark of The Duriron Company, Inc.
*An improved version of this alloy, HASTELLOY alloy C-276, has replaced HASTELLOY alloy C.

Page 7

.13
.03

5
1

mm/y
< .03
.05

mpy
<1
2

<.03
<.03
<.03

<1
<1
<1

Bottom
30
119 (246)
90
mm/y
.15

mpy
6

.05
<.03
.05
.13
.25
28

2
<1
2
5
10
11

41

16

TABLE IV
Comparison of Nickel and Manganese Austenitic
Steels in Organic Acid Exposures
Conditions: Duplicate specimens tested in the boiling
solution (temperatures shown) for 48 hours
or longer. Air not excluded or added.
Corrosion Rate
Temperature
Test Medium
Acetic acid, 100%
Acetic acid, 75%
Acetic acid, 50%
Acetic acid, 25%
Acetic acid 99%;
Acetic anhydride 1%
Acetic acid 90%;
Formic acid 10%
Formic acid, 20%
2-Ethyl butyric
acid, 100%
Esterification
1
mixture

Type 304
Stainless Steel
mpy
.18
160
275
280

CRUCIBLE*
alloy 223

C
117
104
102
100

F
242
219
216
212

mm/y
.46
4.06
6.98
7.11

mm/y
.18
.05
Nil
<.008

117

242

.33

13

2.26

109
102

228
216

.23
1.75

9
69

185

365

.53

86

187

.41

Type 316
Stainless Steel

mpy
7
2
<0.1
0.3

mm/y
.01
.01
.08
Nil

mpy
0.4
0.3
3
Nil

89

.22

8.5

.08
4.75

3.1
187

.17
.56

6.5
22

21

.04

1.5

.04

1.4

16

2.79

110

.02

0.7

(1) Synthetic mixture of 75% butyl acetate, 11% butanol,10% acetic acid, 4% water, 0.3% sulfuric acid.
*Trademark of Colt Industries, Inc.

When molybdenum is added to produce such alloys as


Types 316 and 317 stainless steels, and other alloys, a
remarkable increase in resistance to hot organic acids
occurs. The startling efficacy of molybdenum is best shown
by curves from Uhlig (Figure 2). Note that in the two exposures defined for these curves, the effect of molybdenum
is fully realized at approximately 2.2 per cent. In the vast
majority of organic acid environments, this approximate
amount of molybdenum provides satisfactory corrosion
resistance. For this reason, Types 316 and 316L stainless
steels are utilized for the overwhelming majority of hot
organic acid applications.
Relative values of corrosion resistance for three common
alloys in hot process acid are shown in Table IV to
supplement the data for the Type 316 stainless steel shown
in Table II. Data generated by all major acetic acid
producers confirm that for a pure, uncontaminated acetic
acid of any concentration, Type 316 stainless steel or its low
carbon counterpart Type 316L is usable as a material of
construction to temperatures beyond the boiling point. (See
Effect of Temperature.) These alloys are used extensively in
the fabrication of distillation columns, heat exchangers,
decanters, piping and other apparatus employed in the
production or processing of acetic acid.
Under certain conditions of exposure, it has been found
that additional amounts of molybdenum in the alloy are
beneficial. Types 317 and 317L stainless steels are available
for such applications when required. Tables V through VIII
show process corrosion data where the superiority of the
Type 317 stainless steel can be observed.

Page 8

TABLE V
Corrosion of Alloys in Acetic-Hydroxy Acid Solution
Conditions:

Exposure of approximately 50 days in stripping of acetic acid at temperatures shown


from a 70% acetic acid containing ca. 8%
-hydroxy acids, 20% manganese salts and
residues. Nitrogen blanket on system.
Corrosion Rate
124 C (255 F) 140 C (284 F)

Alloy
Type 304 Stainless Steel
Type 316 Stainless Steel
(annealed)
Type 316 Stainless Steel
(sensitized)
Type 216 Stainless Steel
Type 317 Stainless Steel
Type 326 Stainless
Steel (IN-744)
CARPENTER alloy 20Cb-3
INCOLOY alloy 825
JESSOP alloy JS-700
HASTELLOY alloy G

mm/y

mpy

.01

0.4

mm/y
1.12

mpy
44

Nil

<0.1

.09

3.7

.01
Nil
Nil

0.3
<0.1
<0.1

.11
.05
.08

4.2
2.0
3.2

Nil
.00
.01
Nil
Nil

<0.1
0.1
0.2
<0.1
<0.1

2.84
.05
.03
.01
.01

112
1.8
1.2
0.3
0.4

The effect of further alloying on the corrosion resistance


of commercial alloys is indicated in succeeding sections.

TABLE VI
Effect of Thermal Treatments on Molybdenum-Containing
Stainless Steels
Corrosive medium: Acetic acid 35%, formic acid 1.0%, water 64%.
Conditions
: Process liquid at 131 C (268 F) (boiling) for 84 days, air free.
Corrosion Rate
mm/y
mpy

Alloy

Condition of Specimen

Type 316L Stainless Steel

Annealed
1 hr 677 C (1250 F) AC
4 hr 871 C (1600 F) AC, 1 hr 677 C (1250 F) AC
As-welded (316L rod)
Welded, 1 hr 704 C (1300 F) AC
Welded, 1 hr 871 C (1600 F) AC
As-welded (310 Mo rod)
Welded (310 rod) 1 hr 871 C (1600 F) AC
Annealed
2 hr 621 C (1150 F) AC
1 hr 677 C (1250 F) AC
As-welded (316 rod)
Welded, 1 hr 871 C (1600 F) AC
Annealed
4 hr 593 C (1100 F) AC
1 hr 677 C (1250 F) AC
As-welded (317 rod)
Welded, 1 hr 704 C (1300 F) AC
Annealed
1 hr 677 C (1250 F) AC
1 hr 1316 C (2400 F) AC + 1 hr 677 C (1250 F) AC
As-welded (318 rod)
Welded + 1 hr 704 C (1300 F) AC
Welded + 1 hr 871 C (1600 F) AC

Type 316 Stainless Steel

Type 317 Stainless Steel

Type 318 Stainless Steel

.06
.06
.04*
.08
.08
.07
.06
.06
.39
.39
.65
.40
.71
.05
.16*
.68*
.04
.55*
.07
.07
.64*
.06
.07
.30

2.5
2.5
1.4*
3.2
3.0
2.6
2.3
2.4
15.5
15.3
25.5
15.9
27.7
2.0
6.3*
26.9*
1.73
21.5*
2.6
2.6
25.1*
2.4
2.6
12.0
Reference 11

* Intergranular attack noted


NOTE: AC = Air-Cooled

TABLE VII
Corrosion of Alloys in Acetic-Formic Acid Process Mixtures
Corrosion Rate
Stream
Composition

Test
Temperature Period

Type 316
Stainless
Steel

Type 317
Stainless
Steel

CARPENTER
alloy 20

INCOLOY
alloy 825

HASTELLOY HASTELLOY
alloy C
alloy B

INCONEL
alloy 600

Nickel
200

MONEL
alloy 400

Arsenical
Admiralty

EVERDUR*
1010

100

212

452

03

.03

05

.61

24

.25

10

08

.05

91

196

55

.08

.05

.05

.03

<.03

<1

.10

6% Acetic Acid
10% Formic Acid
3% Water
81% Organics

81

178

55

15

.13

.08

.08

<.03

<1

.10

12% Acetic Acid


3% Formic Acid
85% Water

121

250

355

05

<.03

<1

.05

.08

.03

40% Acetic Acid


6% Formic Acid
5% Water
49% Organics

106

223

99

.51

20

.28

11

38

15

.18

.51

20

.03

17% Acetic Acid


1 % Formic Acid
82% Water
18% Acetic Acid
40% Formic Acid
2% Water
40% Organics

days mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy

*Trademark of Anaconda American Brass Co.

Page 9

sufficient oxidation capacity in the system to maintain a


passive oxide film on the stainless steels. Similar data
obtained in a mixed acid column were presented in
reference 7. Field experience with the equipment confirmed
the validity of the laboratory data. The effect on other types
of alloys of adding oxygen to an acetic acid medium can be
seen in Tables XXII, XXIII and XXV.

TABLE VIII
Corrosion of Metals in Acetic Acid Residue Still
Test Conditions: Test assembly installed in liquid and in
vapor space of still at temperatures of
80 to 100 C (176 to 212 F) for 2000
hours. Residues contain acetic acid,
anhydride, acetates, tar.
Corrosion Rate
Liquid
Alloy

Vapor

mm/y

mm/y

mpy

2.13
.97
2.01
2.01
1.22
.18
Nil
.05
.18
.76
.03
.03

Cast iron
Ni-Resist Type 11
Mild steel
Type 501 chrome steel
Type 430 stainless steel
INCONEL alloy 600
HASTELLOY alloy C
DURIMET* 20
Type 329 stainless steel
Type 304 stainless steel
Type 316 stainless steel
Type 317 stainless steel

mpy
84
38
79
79
48
7
Nil
2
7
30
1
1

1.32
.30
2.51
1.47
.36
.13
Nil
.13
.30
.36
.18
.05

52
12
99
58
14
5
Nil
5
12
14
7
2

.cnI ,ynapmoC noriruD ehT fo kramedarT*

3. Effect of Contaminants
Although pure acetic acid can be handled readily in many
alloys, the presence of only parts per million of other
chemical agents can render an alloy useless as a material of
construction.
Acetic anhydride is produced as a co-product in the
older acetaldehyde oxidation process for acetic acid, and
the anhydride can often be found in other acetic acid
process streams. When small quantities of the anhydride
exist in a glacial acid, a greatly accelerated attack on the
stainless steels can be anticipated. Tables IV, IX and X
incorporate data substantiating the adverse effect of
5
anhydride in acetic acid as reported by Elder and others.
The difference in the two commercial, glacial acids shown
in Table XI can probably be attributed to the presence of
anhydride in the product of Plant B. As the amount of
anhydride in the acid is increased, the rate of attack rapidly
drops to an acceptable level, and high concentrations of
anhydride are innocuous. (See section on Acetic
Anhydride.) However, the presence of small amounts of
anhydride sufficient to dehydrate the acid produces in6
creased attack on all alloys.
Oxygen may influence corrosion rates in acetic acid, and
other organic acids as well. Even though process streams
have been stripped of gaseous components in distillation
systems, the possibility of oxygen pickup from air leaks
into the system is present. The use of stainless steels as
materials of construction assures that no accelerated attack
will occur under such circumstances. Indeed, when corrosion of the stainless steels in a process system is higher than
desired, the rate of attack can often be reduced by
introducing oxygen into the system. Table XLIII shows
the effect of adding oxygen to a distillation column during
the processing of propionic acid. A hundred-fold reduction in the corrosion rate is evident as the oxygen provided

TABLE IX
Corrosion of Type 316 Stainless Steel in Acetic
Acid Solutions Containing Chlorides
Conditions: Duplicate 48-hour tests conducted at the
boiling temperature in glacial acetic acid with
additions made as shown.
Corrosion Rate
Diluent addition
to acid
None
0.2% Acetic Anhydride
0.1 % Water
0.3% Water
0.33% Water
0.50% Water
0.67% Water
1.0% Water

0
mm/y

1.98
.03
.03

.03

mpy

78
1
1

mm/y
.05
1.27**

.08

.03
.18

Chloride Ion Added, ppm*


18
36
mpy
mm/y
2
.43
50**
1.22**

3
.33

1
.66
7
.41

* Added as sodium chloride


** Minute, profuse pitting

Page 10

61
mpy
17
48**

13

26
16

mm/y
2.10
1.19**

.71

.38
.36

mpy
81
75*

28

15
14

Peracids or other per compounds are often formed in


the reaction step of most oxidation processes designed to
produce acetic acid. Peracetic acid is the common,
strongly oxidizing compound formed although various
other per compounds can be produced. The per compounds
act similarly to oxygen in the system. Thus, the stainless
steels again provide good stability in such media and can
often be stabilized by the addition of such compounds.
The effect of adding a peroxide to acetic acid can be noted
in Tables XII and XLIII.
Iron, copper, manganese and similar salts present in an
operating system can serve as powerful oxidizing agents if
in the higher valence state. Such salts quite often accumulate in portions of a system from corrosion products
or as carry-over from the reaction catalyst system. As long
as the anion of the salt is an acetate, such as in ferric
acetate, the presence of these compounds is normally
beneficial to the stainless steels. However, the data of
Table XII would suggest that a thorough investigation
should be made if ferric ion is present at high temperatures. The presence of the ion in these tests actually
accelerated the attack. Cupric ion is particularly effective
as an oxidizing ion, and occasions arise in the processing
of acetic acid solutions in stainless steel equipment where
the addition of cupric acetate is advantageous in reducing
attack on the stainless steel and maintaining passivity of
the surface. Rabald cites the efficacy of mercuric salts in
eliminating attack on a Type 304 stainless steel in glacial
8
acid.
The presence of the reduced (ous) state of these cations
shows no effect on the corrosion rate of the stainless steels
or other metals and alloys.
Chlorides can be considered as the major hazard when
processing acetic acid in stainless steels. Acid contaminated with chlorides can produce pitting and rapid stresscorrosion cracking of the 300 series stainless steels in
specific areas of the equipment. Greatly accelerated,
general corrosion can also ensue if the chloride content is
sufficiently high. Tables IX and X reveal the effect of
chloride ion added as sodium chloride. It will be seen that
a concentration of less than 20 ppm can be allowed before
the rate of attack on Type 316 stainless steel is intolerable.
These data correlate well with the data of reference 7 that
no more than 25 ppm of chloride is permissible before
excessive attack occurs at the boiling temperature. It is
assumed that increasing amounts of hydrochloric acid are
formed as the weak acid is heated over prolonged periods
with the strong acid salt. Where small quantities of
chloride salt in a process steam are allowed to accumulate
and concentrate in process equipment, the effect can be
disastrous for the stainless steels. Both pitting and excessive overall attack on the stainless steels may occur. The
last line of data of Table X is suspect in that the Type 316
stainless steel maintained passivity throughout the test
period. This result is in conflict with the data of the last
line in Table IX. It is believed that Table IX provides a
more accurate description of the effect of chlorides in the
presence of water. Pitting of the stainless steel would
ensue also if the test period were extended.

TABLE X
Corrosion of Alloys in Contaminated Acetic Acid
Condition: Duplicate tests of 120 hours conducted at
the boiling temperature with additions made
as shown.
Corrosion Rate
Test
No.
1
2

Type 316
CARPENTER
HASTELLOY
Stainless Steel alloy 20Cb-3
alloy C
Test Medium
mm/y mpy
mm/y mpy mm/y mpy
Glacial acetic acid
.08
3
<.03
<1
Nil
Nil
(1) + 0.1 % Acetic
.94
37
.84
33
.03
1
Anhydride

(2) + 0.1% Sodium


Chloride

1.32

52

1.07

42

.03

(1) + 0.1% Sodium


Chloride

1.73

68

1.47

58

.03

(4) +1% Water

.03

.03

.03

TABLE XI
Corrosion of Type 316 Stainless Steel in
Acetic Acid Solutions
Conditions: Coupons exposed in hot wall tester to
glacial acetic acid from Plant A and Plant B
with the additions shown.
Acid
Tested

Addition

Exposure
Period

Specimen
Wall
Temperature

hr
Plant A

(None)

Plant A

1%water

Plant A
Plant A
Plant B

0.5% formic
1.0% formic
(None)

Plant B

1 % water

48
96
68
92
48
48
68
96
48

136
146
132
131
137
141
149
152
140

277
295
270
268
278
286
300
306
284

Corrosion
Rate
mm/y
.23
.10
.03
.03
.03
<.03
7.80
12.55
.03

mpy
9
4
1
1
1
<1
307
494
1

Note: All coupons pitted to some extent under all conditions.

TABLE XII
Corrosion of Type 316 Stainless Steel in Acetic Acid with
Additives at Higher Temperatures
Conditions: Laboratory tests in glacial acetic acid contained in pressure autoclaves at temperature
shown for multiple runs of 48 hours each. Data
averaged. Additions to the acetic acid made as
shown.
Corrosion Rate
Additive
None
1500 ppm
hydrogen peroxide
3000 ppm
hydrogen peroxide
3000 ppm H 2O2 +
1500 ppm
Fe +++ (a)
1500 ppm Fe+++ (a)
1500 ppm
hydrogen peroxide
*650 C ( 1202 F) for one hour
a = Added as FeOH(C 2H 3 O 2 ) 2

Page 11

Temperature
C
F
190
374

Annealed
Sensitized*
mm/y mpy mm/y mpy
.20
8

190

374

.23

190

374

.08

190
190

374
374

.69
.56

27
22

240

464

.61

24

.89

35

Processes employing halide catalysts in the reaction


system to produce acetic acid must be assessed thoroughly
to determine where the less costly stainless steels can be
used in the process train. Type 316 stainless steel usually
cannot be used in the reaction area or in the first separation
steps. More highly alloyed materials are required. Once the
halide ion is removed, the overhead acid stream from the
distillation train can be processed safely in stainless steel.
(See section on Process and Plant Corrosion Data.)
Stress-corrosion cracking of the 300 series stainless steels
may occur readily in aqueous acidic media containing
chlorides. Presumably the cracking will not occur in a
completely anhydrous medium, but such a water-free system is obtained rarely and some water must be assumed to
be present. Where the chloride-containing acid solution
can concentrate on the surface of stainless steel under
stress, cracking of the metal can occur. Such areas as
gasket joints, crevices and liquid-vapor interfaces in the
equipment are examples of zones where such cracking
(and pitting) often occurs in chloride-containing acetic
acid. Cracking may also occur beneath deposits or at the
base of pits on the surface of the stainless steels. Where
the metal surface is washed continually with fresh liquid,
there is little likelihood of stress-corrosion cracking. If the
process temperature is less than 80-90 C (176-194 F) the
cracking process may be sufficiently slow to allow a
respectable service life for the equipment before failure
occurs. At temperatures below 50-60 C (122-140 F),
stress-corrosion cracking usually does not occur. Stresscorrosion cracking may be avoided by the use of higher
nickel alloys or duplex stainless steels.
With the exception of formic acid, (see Section on
Formic Acid), other contaminants found in the usual acetic
acid process stream only serve to dilute the acid and reduce
the rate of attack. Aldehydes, ketones, esters and higher
acids are in this category.

until excessive rates of attack are obtained. However, CF8M resists the effect of increased temperature quite well
and has potential for use at the 200 C (392 F) temperature.
Field applications utilizing CF-8M pumps in acid near this
temperature confirm the utility of the alloy for handling hot
acid when oxidizing conditions exist.
Table XII shows other data obtained in the upper
temperature region of Figure 1. Note the lower corrosion
rate for a Type 316 stainless steel at 190 C (374 F),
although the test period is longer. Sufficient peroxide
appears to be effective in reducing corrosion, even at these
high temperatures. The presence of ferric ion was detrimental at these temperatures as opposed to the beneficial
effect noted at lower temperatures.
Vapors of the acid at higher temperatures are not
aggressive in the absence of condensation (Tables VIII and
XIV). However, condensation or drippage of liquid on a hot
metal surface can produce excessive attack. In addition,
pitting of the austenitic stainless steels in acetic acid
exposures at the higher temperatures is possible.
It is obvious that careful assessment of the stability of the
300 series stainless steels in an acetic acid environment
must be made before discounting their use at even the
higher temperatures.

TABLE XIII
Corrosion of Nickel-Containing Alloys in Buffered
Acetic Acid at High Temperature
Test Conditions: Specimens exposed in a high pressure
autoclave at temperature of 200 C
(392 F) for 8 days to the following
solution without aeration or agitation:
15% acetic acid plus 19% ammonium
acetate aqueous solution at 250 psi.
Corrosion Rate
Alloy

4. Effect of Temperature
It has been shown that Types 316 and 316L stainless
steels are satisfactorily resistant to attack by all
concentrations of acetic acid to the boiling point and that
Type 304 stainless steel is acceptable for use in all
concentrations of acid less than approximately 90 per cent
to the boiling point. As the temperature is increased
beyond these points, the rate of attack on the stainless
steels in the liquid acid increases, but certainly not as
rapidly as the Arrhenius equation would indicate.
Laboratory and field data presented in Tables V and XI
through XIII show that for both wrought and cast alloys
the stainless steels remain useful at temperatures well
above the atmospheric boiling point. Various techniques
of testing can produce significantly different results and
ingenuity is required to establish stable conditions for the
desired test environment.
Figure 1 condenses considerable data generated by
Ohio State University personnel when exploring the
corrosion resistance of the cast alloys in acetic acid up to
9
200 C (392 F). The cast CF-8 alloy corrodes at increasingly greater rates as the temperature is increased

Page 12

mm/y

mpy

HASTELLOY alloy C-276

02

0.6

INCONEL alloy, 625

02

0.7

INCOLOY alloy 825


HASTELLOY alloy G
Nickel 200
IN-862 Cast Alloy

02
03
04
05

0.8
1.0
1.5
1.8

Type 315 Stainless Steel (sensitized)

13*

5.2*

Type 316 Stainless Steel (annealed)

04*

1.5*

*Incipient pitting

TABLE XIV
Corrosion of Stainless Steels in Vapors Over 52 Per
Cent Aqueous Acetic Acid at High Temperature

Temperature

System
Pressure
psig

Corrosion
Rate

Alloy

Type 304 Stainless Steel

142

288

35

mm/y
.03

Type 304 Stainless Steel

153

308

55

.10

Type 316 Stainless Steel

142

288

35

<.03

<1

Type 316 Stainless Steel

153

306

55

.05

Each datum is average of eight tests conducted in closed pressure vessel.

mpy
1

Previous comments regarding temperature were in


reference to the bulk temperature of a liquid or vapor in
contact with a metal surface at essentially the same
temperature. These conditions do not exist in heat exchangers, calandrias and interchangers of an acetic acid
process. When a metal surface at a higher temperature is
used to evaporate the acid, higher corrosion rates occur
than obtained isothermally. One explanation is that the
constant heating and cooling of a heat exchanger surface
cracks the protective oxide film on a stainless steel to
expose active metal. Also, ebulition of the liquid at the
surface supplies a mechanical force to dislodge the film.

Decomposition products of organic compounds can form


on the hot surface. Lastly, any corrosive heavy ends in the
liquid can concentrate at the surface to attack the metal, or
tars can form over the metal to produce crevice corrosion in
a random configuration. For these reasons, an actual heat
exchange test should be conducted in any questionable
mixture.
10
Groves, et al. have described a simple apparatus for
conducting heat exchange hot wall tests. Their data are
reproduced in Table XV and illustrate the significant
increase in attack which occurs on an alloy when using the
surface as a heat exchange medium. Further use of this

TABLE XV
Corrosion by Acetic Acid Under Heat Transfer Conditions
Temperature
Without
Heat Transfer
Test Medium
Acetic Acid
10%

50%

99.6%

Corrosion Rate

With Heat*
Transfer

Type 304
Stainless
Steel

Type 316
Stainless
Steel

CARPENTER
alloy 20 Cb-3

HASTELLOY
alloy B

INCONEL
alloy 600

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

101

102

118

214

216

244

110
125
140

110
125
140

110
125
140

230
257
284

230
257
284

230
257
284

<.03
<.03
<.03
<.03
3.30
5.33
5.59
6.35
1.75
6.60
8.64
51

<1
<1
<1
<1
130
210
220
250
69
260
340
20

<.03
<.03
<.03
<.03
<.03
<.03
<.03
<.03
<.03
<.03
33
.25

<1
<1
<1
<1
<1
<1
<1
<1
<1
<1
13
10

<.03
<.03
<.03
<.03
<.03
.05
.08
<.03
.18
.13
.05
2.54

<1
<1
<1
<1
<1
2
3
<1
7
5
2
100

.08
.18
.15
.10
.13
.13
.05
.05
<.03
.18
.18
.08

3
7
6
4
5
5
2
2
<1
7
7
3

.51
.71
.69
.20
1.24
1.12
.79
36
.56
.91
1.14
.36

20
28
27
8
49
44
31
14
22
36
45
14

MONEL
alloy 400
mm/y

mpy

51
1.30
580
14.73
>25.40 >1000
>25.40 >1000
76
1.93
120
3.05
145
3.68
130
3.30
1
.03
120
3.05
68
1.73
220
5.59

*Metal temperature
Reference 10. See that publication for apparatus and technique used.

TABLE XVI
Corrosion with Heat Exchange in Aqueous Acetic Acid Containing Additives
Test Conditions: Apparatus and procedure same as described in Reference 10. Metal temperature 110 C (230 F) with bulk liquid temperature of 100 C (212 F). Test periods
of 4 to 96 hours used. All results
represent duplicate specimens.
Corrosion Rate
Type 304
Stainless
Steel

Type 310
Stainless
Steel

Type 316
Stainless
Steel

Type 329
Stainless
Steel

CARPENTER HASTELLOY
alloy 20 Cb-3 alloy C-276

AMBRALOY*
901

MONEL
alloy 400

Test Medium
Acetic
Acid Additive
56% 1% H 2 SO 4

mm/y
36.07

mpy
1420

mm/y
Nil

mpy
Nil

mm/y
5.8415.24

mpy
230600

mm/y
Nil80

mpy
Nil30

mm/y
64

mpy
25

mm/y

mpy

mm/y

mpy

mm/y
.23

mpy
9

56%

5% H 2 SO 4

22.35

880

Nil61.57

Nil24 24

76.63

3017

5.72

225

17.93

706

36.58

1440

.91

36

25%

4% Formic
Acid

28.83

1135

50.8

200

.71

28

Nil

Nil

Nil

Nil

Nil

Nil

1.17

46

*Trademark of Anaconda American Brass Co.


Reference 43

Page 13

same technique provided the data of Tables XI and XVI.


Table XI illustrates the important point that all glacial
acetic acid is not necessarily the same. This fact is
particularly noticeable when comparing two different
acids by means of the hot wall test. Also note that again
a small amount of water in the acid is most helpful in
reducing attack on the stainless steels. The water is most
effective in this respect regardless of the mode of testing,
and field work verifies this inhibitory effect. The effect of
adding sulfuric or formic acid to the acetic acid is shown
in Table XVI. Notice the accelerating effect of only a
small amount of formic acid added to the acetic. Such an
addition would produce no increase in corrosion of Type
316 stainless steel in an immersion test conducted at
110 C (230 F). The effect of adding the even more
aggressive, higher boiling sulfuric acid, such as used in an
esterification reaction, may be catastrophic as can be
observed from the data.
5. Effect of Microstructure
The austenitic stainless steels are subject to specific types
of attack when exposed to hot organic acids in the same
manner as that observed in the mineral acids. Adverse
mill treatments, fabrication heating cycles, post-fabrication heat treatment and welding can produce changes in
the alloy structure which greatly reduce the corrosion
resistance in hot acetic acid.
Chromium depletion associated with carbide precipitation along the grain boundaries (sensitization) on heating
an unstabilized, regular carbon (0.08 C max) stainless
steel within the range of 425-760 C (800-1400 F) gives
rise to intergranular attack when the alloy is exposed to
hot, concentrated acetic acid. Severe intergranular attack
can result in the phenomenon known as sugaring or
grain dropping. The attacked, heat-affected surfaces are
left in a very rough condition with a bright, (sugary)
faceted surface. If the alloy is sensitized throughout its
thickness, such attack may proceed until the entire thickness of the metal is penetrated.

TABLE XVII
Corrosion in Acetic Acid Vaporizer
Field Test: 312 hr, 140 C (284 F) mass temperature.
Chlorides present
Corrosion Rate
Alloy
Type 316 stainless steel, annealed
sensitized
Type 304 stainless steel
CARPENTER alloy 20Cb-3
INCONEL alloy 600
Titanium
HASTELLOY alloy C-276
*Dissolved
**Pitting

mm/y

mpy

8.13
320
6.86
270
33.02 min* 1300 min*
6.35
250
6.60
260
.08**
3**
.08
3

Persons evaluating the possible effects of sensitization


of an alloy in a specific environment should be aware that
a comparison of weight loss measurements between sensitized and annealed specimens of the metal are not always
an adequate procedure after organic acid exposures. Little
difference in weight loss may be noted between the two. In
fact, many data indicate that the mass of the austenite
grain in a sensitized metal becomes cathodic to the grain
boundary which results in a tower overall loss in weight
than for the annealed structure (Table XVII is typical).
Unless obvious sugaring or the dropping of grains from
the metal has occurred, the welded or sensitized corrosion
test specimen should be evaluated by bending to open and
expose the attack, by ringing to determine if the metal
has lost the characteristic metallic tone, by conducting
magnetic permeability tests, or preferably by a metallographic examination of a cross section of the metal to
observe the type and extent of any selective attack on the
structure.
Susceptibility of the austenitic stainless steels to this
type of attack may be avoided by utilizing a low carbon
grade (.03 C max) or restricting the use of regular carbon
grades (.08 C max) to the annealed condition, without any
subsequent heating into the sensitizing temperature range.
With low carbon grades, there is little likelihood of
sensitization developing in the alloy during welding or
heat treatments. A stabilized counterpart to Type 316
stainless steel known as Type 318 stainless steel is now
obsolete because present melting technology can readily
attain low carbon levels on a routine basis.
The exposure of the chromium-nickel-molybdenum
stainless steels after various thermal treatments to a
process stream containing acetic acid has been reported by
11
the Welding Research Council. (Table VI.) The corrosion
rates obtained were high for such an exposure for reasons
not detailed in the stream analysis. Also, the higher
corrosion rates exhibited by the Type 316 stainless steel
are in conflict with the usual data obtained when
comparing the alloy with the Type 316L alloy. However,
the data are emphatic in pointing out the effect of adverse
heat treatments on susceptible materials. Note particularly
the adverse effect of solution annealing followed by a
sensitization treatment on the columbium-stabilized Type
318 alloy. This type of treatment can occur during multiple-pass welding and may result in knife-line attack on
stabilized alloys.
Although carbide precipitation is the best known and
most common cause of intergranular attack on the stainless steels, certain other metallurgical phenomena must be
recognized as presenting potential problems as a result of
fabrication procedures. The formation of sigma phase or
chi phase in the alloy can be as devastating as carbide
precipitation under certain conditions of acetic acid exposure. Welding alloys such as Types 316L and 317L
stainless steels presents no problems when using solid
construction. However, as the process pressure increases
and the use of clad construction is indicated to be
economically desirable, problems can be encountered if
adequate precautions in the fabrication of the vessel are

Page 14

not observed. Type 316L stainless steel, when heated for


prolonged periods in certain temperature regions above
500 C (932 F), can produce sigma or chi phase in the
alloy. Type 317L stainless steel with higher molybdenum
con-tent is slightly more prone to formation of these
phases. These phases are rich in chromium (chromium and
molybdenum in the case of chi phase) and can have much
the same effect as the more commonly known M23C6 and
M6C carbide precipitation in the alloy. Such a metallurgical phase change can occur in the fabrication of the clad
vessel when it becomes necessary to stress relieve the steel
backing. At the 500-650 C (932-1202 F) stress relief
desired, sigma or chi phase can be produced to create
severe corrosion of the clad material on the interior during
process operations. Lower stress relieving temperatures are
required to avoid such an undesirable metallurgical
condition if these grades of stainless steel are to be used.
6. Quality Control
Qualification tests are often used to assure that the initial
material is of proper quality and that any heat treatment of
the equipment has not produced undesirable effects.
Clippings from sheet and plate, small sections of tubes
and other small sections removed from pieces of equipment are sent to the laboratory for validation of the
existing condition of the material and its ability to maintain
appropriate corrosion resistance. These qualification tests
have been standardized by the American Society for
Testing and Materials (ASTM) and are divided into
practices A through E of Recommended Practice A 262.
Each of these is designed to detect specific types of phase
formation in the alloy. Of these, Practice A, the electrolytic
oxalic acid etch (EOAE) test, is the most sensitive.
Normally, if a heat of stainless steel fails to pass the EOAE
test, samples are tested in accordance with one of the other
practices before rejection of the heat is allowed. However,
because of the sensitivity of the EOAE test, some workers
have advocated that acceptance or rejection be based upon
this test alone to assure maximum corrosion resistance in
the alloy. Major losses in equipment and even more
expensive, extended periods of downtime may be avoided
by these simple procedures.
Castings to be used for pumps, valves and other critical
parts of the equipment can be tested in the same manner.
Solution annealing of castings is mandatory to assure the
optimum corrosion resistance desired. Small amounts of
ferrite provided in the matrix to assure crack-free castings
of the best strength and quality are not harmful. However,
carbides and other constituents which might be isolated
along the dendrites of a casting should be in solution to
prevent selective attack of such areas.
The quality control program for assuring that the
stainless steels used in acetic acid manufacture meet
specification requirements is sometimes extended to
qualitative chemical analysis by means of spot testing of
all material received by the fabricator of the equipment and
by those in the field responsible for installing piping,
heat exchangers, vessels and all other equipment to be
exposed to the hot acid to help assure the proper grade of

stainless steel has been supplied. The molybdenum spot


test is most often utilized in this regard. The cost of such a
procedure is appreciable, but becomes insignificant in
comparison with the failure of a piece of equipment once
the unit is in operation. Simple items such as the drain plug
in a pump, a welding elbow in a hot acid line, a few
incorrect tubes in the heat exchanger and many other small
items can create disastrous problems if an inadvertent
substitution of a lower grade of stainless steel has been
made for the Types 316 or 316L analysis identified for the
use. A materials identification procedure on the site to
provide assurance of proper alloy installation is very easily
justified economically. Kits are commercially available
with complete instructions for doing such work on the site
very quickly and easily. One person assigned to this work
throughout the life of a project may pay for the services
many times over.
C. Martensitic and Ferritic Stainless Steels
The standard AISI grades of martensitic and ferritic
stainless steels generally do not possess sufficient corrosion resistance for use in acetic acid service, except
possibly at low concentrations and temperatures. Table
XVIII shows typical corrosion data for the martensitic
Type 410 stainless steel. Included for comparison are steel,
cast iron and a nickel alloyed cast iron. When evaluating
these materials for an application, it is important to assure
that the service conditions are reproduced as closely as
possible. Laboratory tests can show a considerable
disparity in results because of the possibility of forming a
fragile protective film on the alloy in a short time. After a
high initial rate of attack, the rate will subside to a low
value if the film is undisturbed by flow or other
mechanical effects.
D. Duplex Austenitic-Ferritic and Precipitation
Hardening Stainless Steels
Duplex structured austenitic-ferritic stainless steels and
certain precipitation hardening stainless steels can show
remarkable resistance to organic acids depending on the
ratio of nickel to chromium and other minor alloying
constituents. Table XIX illustrates the resistance of several
precipitation hardening stainless steels in acetic acid at
various temperatures. It is important to understand that the
selection of such alloys for a specific application is more
critical than when appraising an austenitic stainless steel.
Prior processing of the alloy can have a significant effect
on the corrosion resistance. The influence of heat
treatment on the corrosion resistance of three precipitation
hardening stainless steels in acetic acid is shown in Table
XIX. It is obvious that the metallurgical condition of the
alloy must be known when considering these alloys for
acid service. Certain treatments of the alloys can greatly
reduce their corrosion resistance. The data also reveal the
borderline passivity of these alloys in such service, particularly in the intermediate concentration of acid. The
effect of heat treatment on the molybdenum-containing

Page 15

TABLE XVIII
Corrosion of Alloys in Acetic Acid
Corrosion Rate
Per Cent
Acetic Acid
5
5
10
20
20
20
25
25
25
30
40
50
50
60
75
75
75
95
95
99.9
99.9
99.9
100
100
100
100
100

Temperature
C
F
25
99
25
25
100
116
25
104
116
116
116
25
116
110
25
65
116
25
116
25
116
90
25
35
50
100
116

77
210
77
77
212
241
77
219
241
241
241
77
241
230
77
149
241
77
241
77
241
194
77
95
122
212
241

Cast Iron
mm/y
mpy

254

27.69

2.03

20.07

Type 410
Stainless Steel
mm/y
mpy

Carbon Steel
mm/y
mpy

.25*
10,000
57.15

.20*

127

.20*

1,090

7.62

1.02

16.51

.76

12.7

6.86

1.65
80
1.70

1.7811.18

790

10*
2250

8*

5000

8*

300

40
650
30
500
270
65
67
70440

1.274.86

.01

50585

0.3

Type 430
Stainless Steel
mm/y
mpy
<.03

<.03
<.03
3.05
4.27

.38
.25
<.03
<.03
<.03
1.027.62

1.02
1.27

6.86

Nil

1.27
.645.08

<1

<1
<1
120
168

15
10
<1
<1
<1
40300

40
50

270

Nil

50
25200

Ni-Resist
Type 2
mm/y mpy
.91

.53

.58

1.96

1.68

.53

36

21

23

77

66

21

Data combined from various published articles and private communications.


*Rates obtained under quiescent conditions. Removal of the corrosion film will greatly increase the rate of attack.

alloy is particularly critical and must be thoroughly understood when appraising the alloy for acid services.
Duplex stainless steels can also exhibit good corrosion
resistance in acetic and other organic acid environments.
Type 329 stainless steel and cast ACI CD-4MCu are
examples. Tables II, III, VIII, XVI and XXVIII show the
excellent corrosion resistance evidenced by these alloys in
certain specific exposures. These alloys are also more
sensitive to changes in environment than are the austenitic stainless steels. However, in the proper application,
the alloy can exhibit good stability while providing resistance to stress-corrosion cracking. It is for this latter
reason that the duplex alloys are sometimes appraised for
organic acid use.

E. Iron-Base Nickel-Chromium-CopperMolybdenum Alloys

are some rare cases where the corrosion resistance of these


alloys is no better than Type 316 stainless steel, but usually
they provide a higher plateau of corrosion resistance to hot
organic acids. The higher cost of these materials requires
that their area of use in a process be pinpointed and
justified by longer service life.
The cast and wrought alloys of this category are essentially the same in chemical resistance although some small
difference may be noticed in a specific environment. The
cast alloys are exemplified by ACI CN-7M. There are
many proprietary alloys of this general type which bear
trade names. Quite often the designation ends with the
number 20, and indeed this group of alloys is known to
many as the type 20 alloys. Alloys included in this
category are: wrought CARPENTER* alloy 20Cb-3 and
cast DURIMET** 20, ALLOYCO*** 20, WORTHITE**** and others.

When an acetic acid environment is too corrosive for


utilization of Types 316 or Type 317 stainless steels, the
next group of materials usually considered are the ironbased alloys containing higher percentages of nickel and
chromium with molybdenum and copper added. There

Page 16

* Trademark of Carpenter Technology Corporation


** Trademark of The Duriron Company, Inc.
*** Trademark of Aloyco Inc.
**** Trademark of Worthington Corporation

The superiority of this class of alloy may be noted by


reference to Tables II, V, XXVII and XXIX. Particularly
when the acid is contaminated with agents inimical to the
use of Type 316 stainless steel, these alloys usually
provide significant improvement in resistance. For hot
acid pumps, the CN-7M composition shows greater
resistance to erosion-corrosion than CF-8M castings and is
often used in installations that are otherwise entirely of
Type 316L stainless steel construction.
The higher nickel content of the type 20 alloys
provides a fully austenitic structure, imparts good strength
with ductility, is in optimum ratio with the chromium for
maximum corrosion resistance in the iron-base alloys and
increases the resistance of the alloy to chloride stresscorrosion cracking considerably. The wrought or cast
type 20 alloys will not crack in many environments
which produce stress-corrosion cracking in Type 316
stainless steel. The type 20 alloys are susceptible to
sensitization as described for the 300 series stainless steels
unless stabilized or solution annealed. Low carbon contents or the addition of columbium is used to combat the
problem. Knife-line attack may sometimes occur along
beads of multiple-pass welds in the metal-stabilized
alloys. Castings should be used in the solution annealed
condition.

F. Nickel-Base Chromium-IronMolybdenum-Copper Alloys


The nickel-base Cr-Fe-Mo-Cu alloys such as HASTELLOY* alloy G and INCOLOY** alloy 825 are generally
equivalent to 316L stainless steel in mild acetic acid
*Trademark of Cabot Corporation
** Trademark of the Inco family of companies

Black, Sivalls and Bryson Inc. utilize a number of different alloys to


resist various corrosives in its extensive line of rupture disks. Included
are Alloys 400, 600, and HASTELLOY alloy C-276 as well as Type 316
stainless steel and other high nickel alloys to insure reliability.

environments and far superior to Type 316L stainless steel


in the hotter, more aggressive organic acid environments.
This is shown in Tables V, VII, XII1, XXVII, XXVII and
XXX. Their superiority is also indicated in later sections of
this bulletin. (See Tables LI, LVIII, LXVII, LXXIV and
LXXVIII.)

TABLE XIX

Average Corrosion Rates of Precipitation Hardening Stainless Steels in Acetic Acid


Acetic Acid Concentration
100%

75%

50%

25%

Corrosion Rate
Alloy
Type 430
Type 304
PH15-7Mo (as received)b
PH15-7Mo (Al 750)
PH15-7Mo (TH1050)
PH15-7Mo (RH950)
17-7PH* (as received)
17-7PH (A1750)
17-7PH (TH1050)
17-7PH (RH950)
17-4PH* (as received)
17-4PH (H900)
17-4PH (H1025)
17-4PH (H1150)

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

4.90
.43
<.03
08
08
08
30
38
28
25
25
28
33
23

193
17
<1
3
3
3
12
15
11
10
10
11
13
9

1.32
2.21
.05
<.03
30
18
46
10
03
05
15
03
25
05

52
87
2
<1
12
7
18
4
1
2
6
1
10
2

7.67
<.03
03
<.03
71
56
28
28
<.03
08
<.03
<.03
<.03
<.03

302
<1
1
<1
28
22
11
11
<1
3
<1
<1
<1
<1

4.27
<.03
<.03
<.03
76
51
<.03
<.03
<.03
.05
<.03
<.03
<.03
<.03

168
<1
<1
<1
30
20
<1
<1
<1
2
<1
<1
<1
<1

a. Average of duplicate specimens for three 48-hour exposure periods in boiling acid.
b. Heat Treatment A = Annealed
T = Transformation near 760 C (1400 F)
H = Hardening between 482-593 C (900-1100 F) of T or R material
R = Refrigerate treated to 73 C (100 F)
*Trademark of Armco Steel Corporation

Page 17

TABLE XX

Corrosion of the HASTELLOY and Associated Alloys in Acetic Acid


Tests of 120 hours duration at the temperature shown.

25 C (77 F)
mm/y

Medium
10% Acetic Acid
HASTELLoy alloy B
HASTELLoy alloy C
HASTELLoy alloy D
HASTELLoy alloy N
HAYNES* alloy No. 25
MULTIMET* alloy
50% Acetic Acid
HASTELLOY alloy B
HASTELLOY alloy C
HASTELLOY alloy D
HASTELLOY alloy N
HAYNES alloy No. 25
MULTIMET alloy
99% Acetic Acid (Glacial)
HASTELLOY alloy B
HASTELLOY alloy C
HASTELLOY alloy D
HASTELLOY alloy N
HAYNES alloy No. 25
MULTIMET alloy

mpy

Corrosion Rate
66 C (151 F)
mm/y

mpy

Boiling
mm/y

mpy

.01
.01
.02
.03
Nil
Nil

0.5
0.2
0.6
1
Nil
Nil

.15
.01
.23
.07
Nil
Nil

6
0.2
9
2.7
Nil
Nil

.02
.01
.05
.03
.00
.00

0.7
0.4
2
1.2
0.1
0.1

.03
.00
.08
.03
Nil
Nil

1
0.1
3
1
Nil
Nil

.10
.00
.46
.06
Nil
Nil

4
0.1
18
2.5
Nil
Nil

.01
.00
.08
.04
.00
.00

0.4
0.1
3
1.7
0.1
0.1

.00
.01
.01
02
Nil
Nil

0.1
0.2
0.5
0.7
Nil
Nil

.01
.00
.13
.02
Nil
Nil

0.5
0.1
5
0.7
Nil
Nil

.01
.00
.02
.02
Nil
.00

0.2
0.1
0.9
0.8
Nil
0.1

*Trademark of Cabot Corporation

Reference 45

G. Iron-Base Nickel-ChromiumMolybdenum Alloys


There are several proprietary alloys of approximately
25Ni-21Cr and 4 to 6.5 per cent molybdenum that were
developed mainly for resistance to localized attack such as
pitting and crevice corrosion in chloride environments.
Included among these alloys are wrought JESSOP* alloy
JS-700, HAYNES** alloy 20 Mod, ALLEGHENYLUDLUM*** alloy AL-6X and cast IN-862. Judging by
their composition, their corrosion resistance in acetic acid
and organic acids generally should be superior to Type
316 stainless steel in many halide contaminated environments. Unfortunately, data on these alloys are sparse
although some data exist as shown in Tables III, V, XIII,
LXXII and LXXVIII. Note the superiority of alloy JS-700
in the acetic-hydroxy acid solution in Table V and the
freedom from pitting exhibited by cast IN-862 in the
buffered acetic acid solution at 200 C (392 F) shown in
Table XIII. This type of alloy should certainly be
evaluated for aggressive acetic acid environments.
Welded samples of comparable thickness to the equipment
under consideration are suggested for test evaluations
because of the possible formation of sigma or chi phases.

H. Nickel-Base MolybdenumChromium Iron Alloys


Increases in temperature, increases in pressure and a more
complex chemistry in the acetic acid process stream are
characteristics of the more modern processes for producing the acid. In many of these process streams, the
presence of formic acid, higher acids, or halides requires
that the ultimate material of construction in acid resistance, resistance to pitting and resistance to chloride
stress-corrosion cracking be used. The nickel-base alloys
containing molybdenum, iron and chromium are those
materials. The alloys are exemplified by wrought
HASTELLOY alloys C-276 and C-4, INCONEL* alloy
625, cast CHLORIMET** alloy 3 and ILLIUM*** alloys
W1 and W2, among others.
The data in Tables III, VII, VIII, XIII, XV1, XVII, XX,
XXI, XXVII and XXVIII through XXX show the excellent resistance of these alloys to corrosion by hot acetic
acids. In pure aqueous acid streams, or in uncontaminated
glacial acids, the use of these alloys in preference to Type
316 stainless steel is usually not economically justifiable.
However, when impurities are present, they often offer the
most economical choice.

* Trademark of the Inco family of companies


** Trademark of The Duriron Company, Inc.
*** Trademark of Stainless Foundry & Engineering, Inc.

* Trademark of Jessop Steel Company


** Trademark of Cabot Corporation
*** Trademark of Allegheny Ludlum Steel Corporation

Page 18

contaminate an acetic acid stream with halide ions, the use


of the nickel-base, high alloy materials offers the greatest
certainty of economical operation. As discussed under the
effects of contaminants, the presence of chlorides in an
acetic acid stream may produce disastrous results with the
stainless steels. Titanium is also severely attacked when
sufficient chloride ion is present. The copper alloys may
be useful depending on the corrosion allowable in the
system and depending on what other contaminants are in
the stream (e.g., oxygen, heavy metal cations, peroxides,
etc.). The nickel-base alloys containing molybdenum,
chromium and iron are essentially unaffected by such
contaminants. As an example, the data of Table XVII
show the results of a test conducted in an acetic acid
vaporizer using acid contaminated with a small amount of
chloride. The effect on other alloys was severe while the
HASTELLOY alloy C-276 material maintained adequate
stability.

As shown previously, the presence of anhydride in the


acetic acid can render the use of Type 316 stainless steel
unsuitable. Titanium is also attacked by the acidanhydride mixtures (Table XXI). These nickel-base
higher alloys retain immunity to attack in all mixtures of
the acid and anhydride. For this reason, parts of the
distillation columns of the acetaldehyde-to-acetic acid
process were constructed of these high alloy wrought
materials and many of the required pumps were of the
cast counterparts.
When formic acid is a co-product of the oxidation
reaction to produce acetic acid, the process stream can
again be overly aggressive to Type 316 stainless steel
and more highly alloyed corrosion resistant alloys must
be considered for use. If air or other contaminants are
present, the nickel-base molybdenum-chromium-iron alloys are prime candidates as materials of construction.
When the process conditions or operating problems

TABLE XXI
Comparison of Corrosion of Various Proprietary
Alloys in Acetic Acid Solutions
Conditions: Duplicate specimens tested in the boiling solution for 48 hours or longer. Air not excluded or added.
Corrosion Rate
Acetic
Acid,
glacial
Alloy
Type 316
Stainless Steel
INCOLOY alloy 825
IN alloy 102 (A)2
IN alloy 102 (HT)3

50%
10%
30%
Acetic Acid
Acetic Acid
Aqueous
50% Acetic
2%
Acetic Acid
Anhydride
Formic Acid

mm/y mpy mm/y mpy

Esterification
1
Mixture

mm/y mpy mm/y mpy mm/y

mpy

99%
90%
90%
Acetic Acid Acetic Acid Acetic Acid Acetic Acid
1% Acetic
10%
70%
10% Acetic
Anhydride Formic Acid
Anhydride
mm/y mpy mm/y mpy

mm/y mpy mm/y mpy

.01

0.4

1.07

42

.03

<.03

<1

9.12

359

.23

.17

6.5

1.70
<.03
.03
<.03

67
<1
1.1
<1

20.24
.69
.71
.08

797
27
28
3

.36
.15
.10
.03

14
6
4
1

3.66
.18
.18
.28

144
7
7
11

<.03

<1

.08

.03

.28

11

HASTELLOY

<.03

<1

.38

15

.04

1.5

.28

11

alloy C-276
Titanium

<.03

.05

<1
<1
30
25
44
7

1.83

.69
1.19
.91
2.46
.03
.03
<.03

72

27
47
36
97
1
1
<1

6.12

.71
1.14
.05
4.09
.66
.36

241

28
45
2
161
26
14

<.03

.41

<1

16

<.03

.15
.76
.28
.08

<1

6
30
11
3

.05

1.45
.61
.56

57
24
22

1.47

58

.43
.69

17
27

5.84

230

10.67
1.50

420
59

INCONEL

alloy 625 (A) 2


INCONEL

alloy 625 (HT)3

<.03
HASTELLOY alloy D
.76
WAUKESHA * No. 23
.64
WAUKESHA No. 54
1.12
WAUKESHA No. 88
.18
KROMARC ** 55

JESSOP JS-700
4

CARPENTER alloy 20
Multiphase
MP35N***
CROLOY***** 16-1
Chromium Carbide
with 12%
nickel binder
1.
2.
3.
4.

Synthetic mixture of 75% butyl acetate, 11% butanol, 10% acetic acid, 4% water, 0.3% sulfuric acid
Annealed
840 C (1544 F) for one-half hour and furnace cooled
CARPENTER alloy 20 has been superseded by an improved alloy CARPENTER alloy 20Cb-3

*
**
***
*****

Trademark
Trademark
Trademark
Trademark

of
of
of
of

Waukesha Foundry Company


Westinghouse Electric Corporation
Standard Pressed Steel Co.
Babcock & Wilcox Co.

Page 19

TABLE XXII
Corrosion of High Nickel Alloys in Acetic Acid
Corrosion Rate
%
Acetic Acid

Temperature
C

MONEL alloy

Nickel
200

400

F
mm/y
B

mpy

mm/y

30

86

2
2
5
6

70
116
116
26-30

158
241
241
79-86

.03
A
B
.30 ,.05

1
A
B
12 ,2

.28
A
B
1.19 ,.10

11
A
B
47 , 4

10

26-30

79-86

.33A,.08B

13A,3B

.10B

4B

10
10
20
25
30
30
50
50
50
70

70
116
70
26-30
26-30
60
26-30
80
116
116

158
241
158
79-86
79-86
140
79-86
176
241
241

75

26-30

99.9
99.9

mpy

54

.10
.01
.08

4
0.2
3

.02

0.8
13

.36

.05

.33

1.37

600

mm/y

99.9

.03

mpy

INCONEL alloy

14

3.05

120

1.30
A
B
.41 ,.08

51
B
16A,3

3.30
.46
.74A,.10B

18
29A,4B

.05

76-86

.36A,.05B

79-86

.23A,.08B

9A,3B

80

176

130

14A,2B

26-30

116

241

100

26-30
116

241

170A, 10B
66B
19

.15

.13B

5B

.61B

79-86

100

4.32A,.25B
1.68B
.48

24B

.36

14

.10
.30

12

.99

39

A = Aerated
B = Unaerated

Reference 46 primarily.

There are process conditions which require that essentially no corrosion of the material of construction occur.
Critical items of equipment required to operate with close
tolerances such as orifice plates or control valve trim are
examples. Another possibility is that the catalyst system
used in the reactor of the process will not tolerate
contamination with foreign metallic ions. In these cases, the
maximum in corrosion resistance is demanded of an alloy,
and only the nickel-base Mo-Cr-Fe, the nickel-base
molybdenum, zirconium, titanium and tantalum alloys are
potential candidates as solid or clad materials of
construction.
Although the organic acids are less aggressive than
mineral acids in detecting sensitization of this class of alloy,
prolonged exposure of the sensitized alloy in hot acetic acid
can produce intergranular attack. The newer wrought
12
materials, such as HASTELLOY alloys C-276, C-4 and
INCONEL alloy 625 are stabilized to forestall such attack
on fabricated items of equipment. Castings of this type of
alloy should be purchased in the fully solution-annealed
condition. A test for susceptibility to intergranular attack is
defined in reference 13.
These alloys usually provide the ultimate in corrosion
resistance to hot organic acid streams. If the environmental

conditions are such that general attack or pitting of this type


of alloys is excessive, the use of tantalum, zirconium,
graphite and brick-lined construction may be explored.
I. Nickel-Copper Alloys
Alloy 400 and other nickel-copper alloys have very good
resistance to pure acetic acid solutions in the absence of air
or other oxidants. Tables XXII and XXV, among others,
show the low rate of corrosion of MONEL* alloy 400 when
the exposure is free of oxidants. As with other alloys, the
maximum corrosion appears to occur in the 50-70 per cent
acid range. The data agree well with the curve (Figure 3)
published by Uhlig for corrosion of the alloy in acetic acid at
30 C (86 F).
MONEL alloy 400 withstands the effects of oxidants
added to acetic acid better than do either nickel or copper
alone, as shown by Table XXIII. However, the presence of
air or an oxidizing agent such as ferric or cupric ion in
solution is cause for concern and may lead to excessive
attack. Corrosion tests should be run to ascertain the
behavior of these alloys under operating conditions if
oxidants are suspected to be present.
* Trademark of the INCO family of companies

Page 20

The presence of oxidizing agents in an organic acid


stream completely changes the corrosive characteristics of
the medium. Parts per million of oxygen, cupric or ferric
salts, or peracid compounds in the stream will react stoichiometrically with alloys which do not produce protective
oxide films. For instance, copper is essentially immune to
attack by pure, uncontaminated acetic acid. Yet a small
ingress of air at a circulating pump can drive the corrosion
rate in a copper column to > 2.5 mm/y (hundreds of mils
per year). Indeed, copper can be used as a scavenger of
oxidizing species in an organic acid medium and has been
so used.
The addition of nickel to the copper moderates the effect
of oxidants. In general, the greater the amount of nickel in
the alloy, the less the effect of oxygen on the corrosion
rate. This is illustrated by the data of Table XXV. The
addition of nickel to copper appears to have little influence
on the rate of attack in acid contaminated with heavy
metal ions. The accelerating effect of these ions produces
higher rates of attack which remain excessive regardless of
the alloy composition. It is interesting to note the effect of
dilution on the corrosive properties of the various
mixtures. As would be anticipated, the corrosion rate is
greatly accelerated when adding water to an air
sparged solution or one containing ferric ions. However,

FIG 3Corrosion of MONEL alloy 400 in Acetic Acid

The effect of liquid velocity on the corrosion of


MONEL alloy 400 is shown in Table XXIV. No
acceleration of the corrosion rate occurred up to 12.5
ft/sec velocity at a temperature of 30 C (86 F). It is
believed that velocities of this magnitude would not
increase the attack on MONEL alloy 400 up to
temperatures of 100 C (212 F).
Alloy 400 and the cast counterpart of Alloy 400, ACI
M-35 alloy, have found useful service for many years in
some dilute acetic acid solutions handled in the food
industry at the lower temperatures. Alloy 400 is
attractive because contamination of the food products
with ferric or cupric ions is undesirable. Small amounts
of iron can contaminate the products if ferrous alloys are
used and excessive copper pickup can be experienced if
the copper content of the alloy is higher than that of
Alloy 400. Corrosion rates for MONEL alloy 400 in a
typical dilute acetic acid solution of this type are shown
in Table XXII. Mason has covered the subject of the
14
alloys use in food products very well.

TABLE XXIII
Effect of Aeration on Corrosion of Nickel, Copper and
Their Alloys in Acetic Acid
Conditions: Laboratory tests in 6% acetic acid at 30 C
(86 F)
Corrosion Rate
Without Aeration

J. Copper-Nickel Alloys
Alloy

All of the copper alloys excepting those with high (> 15%)
zinc are resistant to acetic acid in the absence of air and
other oxidants. Until the advent of the stainless steels,
copper was used almost exclusively for the handling of
acetic acid.

With Aeration

mm/y

mpy

mm/y

mpy

.08
.05
.08
.08

3
2
3
3

.28
.20
.81
.48

11
8
32
19

Nickel 200
MONEL alloy 400
C 71500 (70-30 Cupro-nickel)
Copper C 10300

Reference 47

TABLE XXIV
Effect of Velocity on Corrosion of MONEL
Alloy 400 in Acetic Acid
Temperature
Medium

50% aqueous Acetic Acid

30

86

Test
Period, hr
48

Aeration
100 cc/min

Velocity
ft/sec

Corrosion Rate
mm/y

mpy

.38

15

.41
.43

16
17

8.7

.41

16

12.5

Page 21

0
1.8
3.8

.46

18

dilution markedly decreases the attack in a solution


containing cupric acetate. This is probably attributable to
the formation of a protective film on the surface, such as a
basic cupric acetate.
Note that the addition of ferric ion as the chloride
produced significantly higher corrosion rates than when
ferric acetate was used as an additive in glacial acetic acid.
A comparison of the effect of the same additives in the 50
per cent acid suggests that the chloride was not mainly
responsible for the greater attack in the 100 per cent acid,
but that the small amount of water added as the ferric
chloride hydrate produced the greater corrosion.
Further evidence that chloride ion does not greatly
affect the corrosion of copper-nickel alloys in organic acids
is shown in Table XXVI. Adding 0.05 to 2.0 per cent
sodium chloride to a synthetic mixture of various organic
acids produced a ten-fold change in the corrosion rate on
copper and the cupro-nickel alloys. However, the rates
remained low enough that copper and copper-nickel alloys

could still be used as materials of construction without a


practical limitation. Increasing nickel content in the alloy
provided no change in the corrosion resistance. Data for
Type 316 stainless steel are provided in this table for
comparison.
The excellent corrosion resistance of the cupro-nickel
alloys in hot acetic acid and the retention of that resistance
in chloride-contaminated acid has significant commercial
implications. The chemical industry around the world has
constructed seashore installations predominantly during the
past 20 years. For such plants, the least costly cooling water
system is the direct use of filtered seawater. The cupronickel alloys are essentially a standard for handling clean
saline cooling water in condensers and other heat exchange
surfaces if compatible with the process stream.
Consequently, in organic acid plants using unpolluted saltwater cooling of condensers, the C70600 alloy (90-10
cupro-nickel) is widely used, and C71500 alloy (70-30
cupro-nickel) and Alloy 400 are used for certain special

TABLE XXV
Corrosion of Copper-Nickel Alloys in Acetic Acid Solutions
Conditions: Quadruplicate specimens exposed in pure aqueous acid solutions for 120 hours at the
boiling temperature except tests without air sparging were extended to 336 hours.
Additives added as shown.
Corrosion Rate

Per Cent
Acetic Acid

Per Cent
Nickel in Alloy

No
Air Sparge
mm/y

mpy

100

0
10
20
30
67
100

.01
.02
.01
.01
Nil
.04

0.4
0.7
0.3
0.2
0.1
1.4

75

0
10
20
30
67
100

.03
.03
.03
.03
.05
.01

0
10
20
30
67
100

.03
.03
.03
.03
.03
.08

1
1
1
1
1
3

25

0
10
20
30
67
100

.05
.03
.03
.03
.03
.15

Air
Sparged
mm/y

mpy

.08
.08
.08
.08
.05
.03

3
3
3
3
2
1

7.87
5.41
4.95
4.78
2.13
1.60

310
213
195
188
84
63

2900 ppm
Fe+++
Added as
Fe(OH)(OAc)2
mm/y

mpy

2100 ppm
Fe+++
Added as
FeCl 3 6H 2 0

mm/y

mpy

mm/y

mpy

51
1.32
2.87
6.15
2.97
81

20
52
113
242
117
32

.25
.30
.28
.25
.18
.13

10
12
11
10
7
5

.76
.76
.74
.74
1.30
5.21

30
30
29
29
51
205

19
31
34
33
36
28

3.28
2.64
2.69
2.36
1.83
1.98

129
104
106
93
72
78

3.00
2.59
2.06
2.46
2.82
4.39

118
102
81
97
111
173

1
1
1
1
2
0.4

50

3200 ppm
Cu++
Added as
Cu(OAc)2

2
1
1
1
1
6

.48
.79
.86
.84
.91
.71

Portion of Data from Reference 48

Page 22

exposures. For a complete description of the excellent


properties of these alloys in seawater, see Guidelines for
15
Selection of Marine Materials. In addition, if mechanical problems arise which allow seawater contamination of
the process stream, such as a leaking condenser tube, the
cupro-nickels and Alloy 400 are not excessively corroded
by the contaminated acid.
K. Nickel-Chromium Alloys
The nickel-chromium alloys represented by Alloy 600 and
ACI CY-40 are little used in the production and handling of
acetic acid. In general, the iron-base alloys with chromium,
nickel and molybdenum exhibit superior corrosion
resistance in the acid streams and economic considerations
dictate no better choice. For certain specific appurtenances
on the major equipment, INCONEL alloy 600 has been
used when required because of availability or to take
advantage of certain mechanical properties of the alloy.
However, these uses have been minimal. The more
corrosion-resistant iron-base nickel-chromium-molybdenum-copper alloys are used to combat stress-corrosion
cracking when the stainless steels are not useful and
forestall any consideration of the nickel-chromium alloys
for the new construction of major items of equipment.
When existing equipment of the versatile nickel-chromium
alloy is available, the processing of various acetic acid
mixtures is permissible if the corrosion characteristics of
the medium have been properly defined. In general, the
lower concentrations of acetic acid (< 60%) in aqueous
solution can be handled without excessive corrosion. If
oxygen is present in the solution, the nickel-chromium
alloy is superior to the nickel-copper or cupro-nickel alloys
in corrosion resistance.
Data showing the resistance of the basic nickel-chromium alloys to corrosion by acetic acid are presented in
Tables VII, VIII, XV XVII, XXII, XXVII, XXVIII and
XXX.

This 15,000 pound capacity reactor kettle of INCONEL alloy 600 was used
for over 27 years for the dehydration or polymerization of castor, linseed
and soybean oils. Alloy 600 was chosen to withstand the corrosive effects
of vegetable oil acids and C 18 fatty acids at a temperature of 600 F.

L. Iron-Nickel-Chromium Alloys
Alloy 800 has fair resistance to hot acetic acid solutions.
The iron and chromium of the alloy dictate that conditions
should be slightly oxidizing to realize the best resistance
from the alloy. However, the alloy cannot compete with
Alloy 825 or other metals containing molybdenum as a
prime candidate for process use.
The good chloride stress-corrosion cracking resistance
of the alloy makes use of the material attractive for small,
specialty applications, but the corrosion rate must be
determined closely to assure that adequate life will be
obtained. As a general statement, the better solution to a
problem involving acetic acid corrosion and chloride stresscorrosion cracking is the use of the type 20 alloys, or the
nickel-base iron-chromium-molybdenum-copper alloys.

TABLE XXVI
Effect of Sodium Chloride in a Mixed Acid Medium on
the Corrosion of Copper-Nickel Alloys
Conditions: Duplicate specimens immersed in a boiling 116 C
(241 F) solution of 60% acetic acid, 10% formic
acid, 10% heavy organic acids and 20% water for
100 hours.
Corrosion Rate

Per Cent NaCI


Added to Acid

C70600
(90-10
Cupro-Nickel)

Copper

C71500
(70-30
Cupro-Nickel)

mpy

Type 316
Stainless Steel

mm/y

mpy

mm/y

mm/y

mpy

mm/y

mpy

0.05

.01

0.4

.01

0.3

.01

0.3

.38

15

0.10
1.0

.01
.08

0.3
3

.01
.05

0.3
2

.01
.08

0.5
3

.56
12.27

22
483

2.0

.10

.08

.10

22.66

892

Page 23

M. Nickel-Base Molybdenum Alloys

Corrosion data for this type of alloy are given in Tables


III, VII, XV, XX, XXVII and XXVIII through XXX.

Greater attention has been given to this class of alloy for


acetic acid exposures in recent years. For most acetic acid
applications, the nickel-base iron-chromium-molybdenumcopper alloys are superior to the nickel-base molybdenum
alloys without chromium. However, HASTELLOY alloys
B and B-2 have good organic acid resistance and have
sometimes been used for the distillation of acetic acid
mixtures. The cast alloys in this family of alloys include
ASTM A 494 grades N-12M-1 and N-12M-2. Trade
names associated with these cast grades include
CHLORIMET alloy 2 and ILLIUM alloys M1 and M2.
These alloys offer excellent corrosion resistance in
certain of the newer acetic acid processes utilizing
chloride catalysts under reducing conditions at high
temperatures. Under these conditions, only zirconium,
titanium, and the nickel-base molybdenum alloys appear
16, 17, 18
to be attractive.
For the high pressures employed for
the reaction area, the use of clad construction is very
attractive.

N. Nickel
Commercial nickel is less resistant to attack by acetic acid
at any temperature than are the nickel-copper alloys, the
cupro-nickel alloys, or the austenitic stainless steels.
Consequently, nickel as a basic material of construction is
not generally used. The material is used as the underbead
in the welding of copper-clad steel, being compatible with
both the copper and the steel backing.
Data showing the resistance of wrought Nickel 200 to
acetic acid under varying conditions are contained in
Tables III, VII, XIII, XXII, XXIIL XXV, XXVII, XXIX
and XXX.
The presence of air accentuates the corrosion of nickel.
For example, Uhlig reports a rate of attack of .02 mm/y
(0.9 mpy) for nickel in a 6% acetic acid solution charged
with nitrogen at room temperature, but a rate of .28 mm/y
19
(11 mpy) when air is introduced.

TABLE XXVII
Corrosion of Metals and Alloys in Acetaldehyde Oxidation
Process for Acetic Acid
Corrosion Rate
Exposure*
Alloy

mm/y mpy mm/y mpy mm/y mpy

10

mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy

ACI CF-8

0.38

15

ACI CF-8M

.03

ACI CN-7M

Nil

0.1

.13

Nil

0.1

.02

0.6

.01

0.4

.01

0.5

Type 446 Stainless Steel

.19

7.5

Type 204 Stainless Steel

.06

2.5

2.54

100 1.70

67

Type 304 Stainless Steel

.09

3.5

1.78

Type 316 Stainless Steel

.06

2.4 2.34

Type 317 Stainless Steel

.02

0.7

CARPENTER alloy 20

.01

0.5

INCOLOY alloy 825

70 1.22

48

2.16

85

.18

.13

.08

.03

.25

10

92

.33

13

.43

17

.05

.03

.03

Nil

Nil

Nil

Nil

.01

0.4

.01

0.5

.01

0.5

.03

Nil

Nil

Nil

Nil

Nil

0.2

.89

35

.18

.20

.05

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

.03

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

HASTELLOY alloy C

Nil

Nil

.03

.03

.03

.03

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

HASTELLOY alloy B

01

0.5

.28

11

.23

.03

.05

.18

.25

10

HASTELLOY alloy D

.1 5

INCONEL alloy 600

.12

4.6

.36

14

.23

Nickel 200

.10

4.1

.86

34

.81

32

MONEL alloy 400

.11

4.4

1.12

44 1.07

42

.94

37

.01

0.3

.03

Nil

Nil

Nil

Nil

EVERDUR 1010 Silicon Bronze

.10

3.9

Copper

.28

11

<.03

<1

DURIRON **

*Exposure
1-Product flash kettle base liquid at 95-100 C (203-212 F) for 737 days. Approx. 58% acetic acid, 40% anhydride, 2% residue with peroxides present.
2-Stripping still kettle liquid at 148-150 C (298-302 F) for 56 days. Approx. 65% acetic acid, 36% anhydride, residues, peroxides and catalyst salts.
3-Liquid of stripping still base section at 120 C (248 F).
4-Vapor of stripping still base section at 120 C (248 F).
5-Liquid of stripping still mid-section.
6-Anhydride still kettle liquid at 145 C (293 F). Essentially anhydride.
7-Anhydride still kettle vapor at 145 C (293 F).
8-Acetic acid refining still base liquid at 145 C (293 F). Mostly anhydride.
9-Acetic acid refining still base vapor at 145 C (293 F).
10-Acetic acid refining still overhead at 120 C (248 F).
**Trademark of The Duriron Company, Inc.

Page 24

Nickel plating appears to have essentially the same


corrosion resistance in acetic acid solutions as the
wrought metal. An increase in corrosion resistance is
reported for electroless nickel which is properly heat
treated. Volokhova, et al. report rates of .10 and .05 mm/y
(4 and 2 mpy) for untreated electroless nickel plate in 5%
and glacial acid, respectively, at room temperature while
specimens of heat-treated plating showed only .01 and nil
mm/y (0.3 and 0.09 mpy) in the same acids.20

tion. Such a situation demands more detailed testing and


economic evaluation of alloys, taking into account not only
first cost but maintenance costs and reliability as well.
a. Oxidation of Acetaldehyde
The oldest of the current processes used for any
significant production of acetic acid is the oxidation of
acetaldehyde. In this process, acetaldehyde is air-blown in a
small tubular converter with distillation of the product and
21 22
recycling of unreacted acetaldehyde to the reactor. ,
The primary converter product contains, in addition to
acetic acid and unreacted acetaldehyde, varying quantities
of acetic anhydride, ester, peracetic acid and catalyst salts
from the converter. As pointed out previously, the presence of the anhydride increases the corrosive nature of the
stream. (See Tables IV, IX and X.) Until the anhydride and
catalyst salts are separated from the acid, a close evaluation
of the corrosion to be expected in all sections of the
equipment is necessary. For instance, the still used
to separate the acid and anhydride may require a nickelbase molybdenum-chromium-iron alloy for the base kettle, the calandria and a few lower sections of the column.

O. Process and Plant Corrosion Data


1. Acetic Acid Production
The modern industrial chemical plant has changed radically during the past few decades. Efficient, economical
production requires large single-train units that put greater
emphasis on the reliability of components. If a failure does
occur, it causes a shutdown of the entire process. When
this happens, production losses will often far overshadow
any differences in cost between alloys of marginal corrosion resistance and more durable materials of construc-

TABLE XXVIII
Corrosion of Alloys in a Hydrocarbon Oxidation
Unit for Acetic Acid
Corrosion Rate
Location *
Alloy
Type 304 Stainless Steel
Type 202 Stainless Steel
Type 316 Stainless Steel
Type 317 Stainless Steel
Type 329 Stainless Steel
CARPENTER alloy 20Cb-3
HASTELLOY alloy G
HASTELLOY alloy C
HASTELLOY alloy B
INCONEL alloy 600
IN alloy 102
MONEL alloy 400
STELLITE alloy No. 3**
STELLITE alloy No. 4
STELLITE alloy No. 6
HAYNES alloy No. 93**
HAYNES alloy 25
ILLIUM B***
ILLIUM P
ILLIUM PD
ILLIUM 98
DURICHLOR****
Titanium
Zirconium
Copper
C70600
(90-10Cupro-Nickel)

mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy

mm/y

mpy

.05

.05
<.03

.10

.13
.05

<.03

2
<1

5
2

<1

.05

<.03
<.03

<.03

.08
Nil
Nil

<1
<1

<1

3
Nil
Nil

.05

.05
<.03

.10

Nil

2
<1

Nil

.03
1
.25

<.03 < 1
.05
<.03 <1

.05
2
<.03

<.03
.10
4

.18
7

.46
18

>2.54 >100

.03
1

<.03 < 1

<.03 <1

<.03 <1

.10
4

.56

* See process diagram Figure 4.


** Trademarks of Cabot Corporation
*** Trademark or Stainless Foundry & Engineering, Inc.
****Trademark of The Duriron Company, Inc.

Page 25

.05

10

<1

<1

22

.03

<.03

.05

.03

<.03

Nil

.69

.10

<1

Nil

27

.05

Nil

.08

Nil

28
.30
<.03
.03

<.03
5.59

3.56

11
12
<1
1

<1
220

140

<1

.05

.10

The middle column sections may require somewhat less


highly alloyed materials, such as the iron-base nickelchromium-copper-molybdenum alloys, while the top portion of the column, the condenser and all associated piping
may be made of Type 316L stainless steel. Returning to
the higher temperatures of the base area, the calandria
circulating pump and other cast appurtenances must be of
a Type CN-7M casting as a minimum, and the use of more
corrosion-resistant alloys or graphite may be necessary.
The remainder of all operating facilities of an
acetaldehyde-based acetic acid unit can normally be constructed of Type 316L stainless steel with Types CF-8M
or CF-3M cast valves and pumps. The anhydride refining
still normally presents no exceptional corrosion problems
for Type 316L stainless steel. Copper, cupro-nickel alloys
and Alloy 400 nickel-copper alloy can be used for any
required applications once the peracetic acid is destroyed
in the system by high temperatures in holding tanks or
column bases and the equipment is sealed from the ingress
of air. Corrosion data obtained in an acetaldehyde
oxidation process unit are tabulated in Table XXVII.
Additional data for a wide range of allays exposed in an
acetic acid residue still of the same process are given in
Table VIII.

b.

Liquid Phase Oxidation of StraightChain Hydrocarbons

Among the important processes of today for acetic acid


production are those based on the direct oxidation of
straight-chain hydrocarbons, such as propane, propylene,
butane, butene and higher aliphatics. The oxidation can be
achieved using air or oxygen. Reaction conditions are
much more severe than for the simple oxidation of an
aldehyde with temperatures near 200 C (392 F) at
pressures of more than 700 psi. Breaking up a hydrocarbon
by such a severe oxidation obviously produces many byproducts in addition to acetic acid. Among these are
formic, propionic, butyric and higher acids, ketones, esters
and peroxide compounds. The reaction conditions of the
converter can be varied to increase or decrease the ratio of
the by-products. This mix of products and by-products
creates two problems not present in an aldehyde oxidation
process: (1) much more separation equipment is required
to recover the products and (2) the corrosion medium is
more complex. Added to this is the large size of the
equipment required for the large volume output of a
modern single-train unit.
A simplified flow diagram for a typical hydrocarbon
oxidation unit is shown in Figure 4. Essentially the entire

TABLE XXIX
Corrosion of Allays in Laboratory Equivalents of the Methanol-Carbon Monoxide Reaction Medium
Conditions: Small autoclave tests for 48 hours using 50%
acetic acid at autogenous pressure without
and with catalyst (7 grams cobalt acetate

hydrate and 7 grams potassium iodide per


100 grams of acetic acid). Carbon monoxide
atmosphere.

Corrosion Rate
Without
Catalyst

Temperature

With
Catalyst

Alloy

mm/y

mpy

Type 304 Stainless Steel


Type 310 Stainless Steel
Type 321 Stainless Steel
Type 347 Stainless Steel
Type 316 Stainless Steel

250
300
250
300
300
250
260
300
250
260
280
260
230
280
260
230
260
230
260
260
260
260

482
572
482
572
572
482
500
572
482
500
536
500
446
536
500
446
500
446
500
500
500
500

>25.4*

>25.4
9.14*
5.08

1.63
3.81

.36

<.03

>1000*

> 1000
360*
200

64
150

14

<1

CARPENTER alloy

INCOLOY

20

alloy 825
alloy C

HASTELLOY

HASTELLOY

Nickel 200
Silver
DURIRON

Titanium
Zirconium
Tantalum

alloy B

*Pitting

mm/y

mpy

2.03

10.16

22.35

5.08

1.78
5.08

.36
71
5.84
3.05
2.67
<.03
<.03
<.03

80

400

880

200

70
200

14
28
230
120
105
<1
<1
<1
Reference 17

Page 26

facility can be constructed of Type 316L stainless steel.


There are certain precautions, however:
The high temperature of the reactor requires that the
Type 316L stainless steel be fully qualified and in its most
corrosion-resistant condition. (See Effect of Microstructure.) Type 316L stainless steel clad construction over a
steel substrate offers the most economy for the high
pressure reactor but the fabrication techniques must assure
that the maximum corrosion resistance of the stainless steel
is retained.
Proper operation of the plant is essential. Although Type
316L stainless steel is resistant to the normal conditions of
operation existing in the reactor, if the temperature reaches
much more than the nominal 185 C (365 F), the corrosion
rate for the alloy increases rapidly.
There have been instances in which weld deposits have
been less corrosion resistant than the base metal, perhaps
because of compositional differences. For this reason, many
welds are made using a more highly alloyed weld rod or
filter wire.
Circulating pumps for the hot process liquid are usually
of a solution treated CN-7M alloy casting. If temperatures
are maintained at lower levels for the reaction, the CF-8M
or CF-3M alloy castings will exhibit a satisfactory service
life.
The acids longer than acetic (propionic, butyric, etc.)
produced in the reaction add little if any to the corrosivity
of the stream, because temperatures of the process
following the reaction are lower than those required to
promote corrosion of the stainless steels by these acids. (See
section on Higher Organic Acids.)

TABLE XXX
Corrosion of Alloys in Synthetic Reactor Product from
Methanol-Carbon Monoxide Process for Acetic Acid
Conditions: Aqueous 70% acetic acid at the boiling temperature 107 C (243 F) without and with
catalyst (ca. 6% cobalt acetate hydrate and
6% potassium iodide). Purged with CO.
Corrosion Rate
Without
Catalyst
Alloy
Type 304 Stainless Steel
Type 321 Stainless Steel
Type 347 Stainless Steel
Type 316 Stainless Steel
24Cr-20Ni-Mo-Cu**
CARPENTER alloy 20
INCOLOY alloy 825
INCOLOY alloy 800
HASTELLOY alloy C
HASTELLOY alloy B
INCONEL alloy 600
Nickel 200
MONEL alloy 400
C71500 (70-30 Cupro-Nickel)
C70600 (90-10 Cupro-Nickel)
Aluminum Bronze
Titanium
DURIRON

With
Catalyst

mm/y

mpy

mm/y ,

mpy

41
.51
1.91
.15
<.03

15
<.03
.48
.53
.18
Nil
Nil

16
20
75
6
<1

6
<1
19
21
7
Nil
Nil

15*
.25*
.33*
.08*
.03*
.23*
.05
.13*
.10*
.20
.38
.33
.41
.94
1.14
2.34
Nil
Nil

6*
10*
13*
3*
1*
9*
2
5*
4*
8
15
13
16
37
45
92
Nil
Nil

* Pitting occurred. Authors correctly reported only observations and


weight loss of coupons. For comparison, the weight loss was converted to corrosion rate on basis of data given.
** Contained 2.3% Mo and 2.0%Cu
Reference 18

Page 27

By-product formic acid adds acidity to the system, but


does not greatly increase corrosion of the stainless steels.
Table VII shows corrosion rates of various alloys in aceticformic acid mixtures typical of those existing in a hydrocarbon oxidation unit, but without peroxides present. As in
other processes for acetic acid production, the peroxides
react with other components of the stream or are decomposed with sufficient time at the higher temperatures. Thus,
the cupro-nickels and Alloy 400 can be used after the
process stream passes the separation column of such a
system, if desired.
Actual corrosion data obtained in the various parts of a
hydrocarbon oxidation unit are shown in Table XXVIII.
Contamination of the process stream with chlorides, metal
salts, or other inorganic materials introduced in the feed
streams or by leakage into the system can have disastrous
effects as noted under the discussion on the effect of
contaminants.
c. Methanol-Carbon Monoxide Synthesis
The methanol-carbon monoxide process is one of the
newer and economically attractive routes for the production of acetic acid. In this process, all factors contributing
to higher corrosion rates are encountereda 50-75% acid
concentration, higher temperatures, higher pressures and
the use of halide salts as catalysts. The use of boron
trifluoride as a catalyst did not become popular because of
the exceedingly high pressures involved, but the use of
iodides in combination with other metallic salts has
increased in popularity throughout the world.
No data directly derived from the field exposure of
alloys in operating equipment of the methanol-carbon
monoxide process are available. However, Togano and
others have delineated the problem facing the corrosion
engineer when materials selection must be made for these
16-18
processes.
The reaction vessel must be made of the
most resistant alloys available. In all probability, the
process stream must be carried through the first two still
columns before the halogen is reduced to a level sufficient
to allow the use of the austenitic stainless steels. Even at
this point, care must be exercised in selecting a stainless
steel because the acid is not derived from an oxygenated
reaction. Thus, no peroxides or oxidizing gases from their
decomposition will be available to aid in passivity of the
stainless steel.
Certain of the higher nickel alloys do appear to have
promise in this process. Tables XXIX and XXX taken
from the Tagano reports show HASTELLOY alloys B and
B-2 to be worthy of thorough testing along with titanium,
zirconium and tantalum for the high pressure, high
temperature reaction area. Once the temperature is reduced to the normal recovery conditions, the use of
nickel-molybdenum and nickel-copper alloys appears attractive even with the catalyst salts present. It also appears
that INCOLOY alloy 825 should be evaluated with close
attention to make sure that the resistance to pitting shown
in Table XXX is consistent. As indicated, once the halide
salts are removed, the conventional materials used for the
separation and recovery of the acid can be employed.

Certain other interesting observations can be found in


references 17 and 18. The catalyst system requires very
high concentrations of catalyst. When half of the catalyst
is a halide salt, the potential for corrosion is greatly
increased. (See Effect of Contaminants.) By comparison
with various other tests, particularly when appraising the
austenitic stainless steels, it is apparent that the iodide ion
is not as aggressive as is the chloride ion.
The authors found no adverse effect of carbon monoxide on the nickel-base alloys at the temperatures and
pressures explored. Indeed, the presence of CO was
reported to reduce corrosion, particularly pitting of ironbase alloys.
2. Acetic Acid Storage and Shipping
Stainless steels are used for the construction of storage
vessels for acetic acid to maintain the highest quality of the
acid. Vessels of the dished-head type, API variety, or
external support construction have been used for this
purpose. The latter has been used extensively in the wine
fields for the storage of wine in the past and provides the
most economical method of fabricating field tanks for acetic
acid storage if the size is not excessive.
When choosing the stainless steel grade, consideration
should be given to the temperature of storage proposed and
to the grade of acid required. In the northern latitudes,
it will be necessary to provide a heating coil to assure fluid

Of the 15 miles of pipe used in this storage terminal for handling


organics, 3 miles are of Type 316 stainless steel. This material protects
the purity of formaldehyde, acetic acid and propionic acid.

Page 28

conditions for the acid (m.p. 16 C or 61 F). For this


service, the coil is usually constructed of Type 316L
stainless steel. Heat transfer on the surface of Type 304
stainless steel can produce excessive corrosion at normal
steam temperatures.
The vessel proper can be constructed of Types 304,
304L, 321, 347, 316, or 316L stainless steels. If a truly
meticulous grade of acetic acid is required, such as USP
grade, it will be necessary to use the molybdenumcontaining grade of stainless steel if temperatures are to
exceed 50-60 C (122-140 F). In this range, a minute
amount of metallic contamination of acetic acid can occur
in contact with the Type 304 analysis or other grades not
containing molybdenum. The use of a molybdenumcontaining stainless steel moves this point of initial
contamination to some 70-80 C (158-176 F) before any
5
detectable metallic ion is picked up by the acids.
When using the stainless steels for tankage equipment in
a meticulous service, it is advisable to clean (pickle,
passivate) the interior of the vessel to remove all traces of
iron contamination that might have been embedded in the
stainless steel at the mill. Sulfamic acid, nitric acid, oxalic
acid, or other acids as suggested by ASTM A 380 can remove the embedded iron and at the same time provide a
uniform clean surface for the stainless steel. Since the
more aggressive acids can cause intergranular corrosion of
sensitized stainless steels, it appears prudent to utilize a
low carbon or stabilized grade if fabrication by welding is
anticipated.
Shipping containers constructed of stainless steel
provide the greatest durability combined with the best
preservation of the refined acetic acid of all materials
available today. Tankers have stainless steel-lined compartments for shipment of the organic acids and other
corrosive products. If entire compartments are not justified
on tankers for conveying the acetic acid, deck tanks can be
added which are durable and free of harmful corrosion in
the severe exposures of marine transportation. Complete
barges have been constructed using stainless steel for
meticulous care of the product during shipment. Tank cars
constructed of stainless steel have been used for 40 years
on the rails for acid shipments as well as to provide the
versatility required for the shipments of other aggressive
commodities.
In the smaller containers, the austenitic stainless steels
remain unparalleled as the material of construction for
drums, cans and other items used for the shipment of
acetic acid. With the higher area-to-volume ratios existing
in the small containers, it is imperative that no corrosion
occur on the container walls to contaminate the acid. For
this reason, the stainless steels constitute standard construction identified as ES and ESM (DOT designation for
Types 304 and 316 stainless steels) drums and cans for
acetic acid shipments. These not only provide good
protection of the acid during long periods of shipment and
storage, but are durable and reusable for many years
because of the good strength and external corrosion
resistance of the stainless steel container. Stainless steel
containers are readily cleaned on the inside to provide a
spotless, uncontaminated surface for reuse.

The forward tanks in this double-skinned barge are clad with Type 316
stainless steel, capable of transporting organic acids as well as other
liquid cargo.

3. Vinegar Production and Storage


All vinegars contain acetic acid in addition to variable
amounts of nonvolatile organic acids such as malic and
citric acids and smaller amounts of succinic and lactic
acids. The term grain strength is used to express the
acetic acid concentration, which is ten times the acetic
acid content. Protection of the vinegar from metal
contamination, particularly iron and copper, has led to the
use of the austenitic stainless steels for both production
and storage. Table XXXI shows that both Types 304 and
316 stainless steels are unaffected in 40-320 grain vinegar
at the -17 to 35 C (2 to 95 F) process temperatures
involved. Because of the low temperatures, intergranular
corrosion of sensitized stainless steel is not a problem.
Although 120 grain (12 per cent acetic acid) is a common
strength, the particular plant at which this test was run
produces up to 300 grain vinegar in Type 304 stainless
steel equipment and piping without corrosion problems or
product contamination.
P. Acetic Anhydride
Acetic anhydride has long been made as a co-product in
the dual oxidation of acetaldehyde to acetic acid. With
the many streams in this process containing both acetic
acid and the anhydride, it is important to understand the
effect of small amounts of anhydride residual in hot acid
streams. However, the anhydride itself is only mildly
corrosive. In the absence of acetic acid, distillation in
Type 304 stainless steel equipment is acceptable.
In the newer process where acetic acid or acetone is
cracked to ketene, which is then reacted with acetic acid to
form the anhydride, it is reported that Type 316 stainless
steel is fully satisfactory for the construction of distillation
columns and other process equipment. However, Type
316L stainless steel is often selected so that the equipment
is more versatile and can be used for other organic acid
services where more stringent conditions might exist.
In the process utilizing acetic acid as the starting
23
material, the cracking tubes are of prime interest. Once

Page 29

TABLE XXXI
Corrosion of Stainless Steels in
Vinegar Production
Corrosion Rate
Test 1
Alloy

Test 2

Test 3

Test 4

mm/y

mm/y

mpy

mm/y

mpy

mm/y

mpy

Nil*
Nil
Nil

Type 304 Stainless Steel


Type 316 Stainless Steel
Type 304 Stainless Steel
sensitized for 1 hour
at 677 C (1250 F)

mpy
Nil
Nil
Nil

Nil
Nil
Nil

Nil
Nil
Nil

Nil
Nil
Nil

Nil
Nil
Nil

Nil
Nil
Nil

Nil
Nil
Nil

*No detectable attack in the form of general corrosion, pitting or crevice corrosion.

Location
Vinegar Concentration
(Grain)
Temperature Range C
F
Test Duration

Test 1
Storage
Tank

Test 2

Test 3

Accumulator

Test 4
Storage
Tank

Freezer

40-66

80-122

50-300

80-320

21-35
70-95

27-34
80-93

17 to 2
2-28

0-16
32-60

all tests 150 days

the acetic acid is fully vaporized, the stream is essentially


innocuous from a corrosion standpoint. However, properties of the cracking tube alloy are significant. The catalytic
properties of nickel can cause breakdown of hydrocarbons
at high temperatures. For this reason, various nickel-free
alloys have been developed (Fe-Cr, Fe-Cr-Al, Fe-Cr-Al-Si)
for use in such services. However, the operating
temperatures of 700-750 C (1292-1382 F) can develop
sigma and other adverse metallurgical conditions in the
iron-chromium alloys. To make furnace operations less
critical and to obtain improved fabricability, the use of cast
austenitic alloys was explored. It was found that the inner
surface of the tubing was rapidly coated with a deposit of
carbon which sealed the process stream from catalytic
effects conferred by the metal surface. Thus, advantage can
be taken of the better ductility and fabricability of the
austenitic alloys for such service. Rates of degradation of
the various alloys caused by the oxidation reactions that
occur in the environment are shown in Table XXXII.
Handling of the acetic anhydride and its dilution with
acetic acid presents no problem other than that described
under the processing of acetic acid. Type 304 stainless
steel is eminently satisfactory for the distillation, storage,
or shipment of the anhydride. Nickel plating showed a nil
rate of attack in acetic anhydride at ambient temperature
during a 121-day test.

TABLE XXXII
Deterioration of Alloys in Glacial Acetic Acid Vapors at
750 C (1382 F)
Average Penetration
Initial Exposure
200 hours
Metal

Second Exposure
100 hours

mm/y

mpy

mm/y

mpy

Type 430 Stainless Steel

.48

19

1.22

48

Type 446 Stainless Steel

.91

36

.18

.41

16

ACI HK Alloy

Type 304L stainless steel equipment and piping and ACI CF-8M valves
for metering acetic anhydride to process kettles. Courtesy Walworth
Company-Aloyco Valves.

Page 30

PART III. OTHER ORGANIC ACIDS


A. Formic Acid
As with other one-carbon homologues of an organic
family, formic acid exhibits unique properties. The acid is
more highly ionized than are most other members of the
group and reacts readily with many oxidizing and reducing
compounds. This potent reactivity is apparent also in the
reaction with metals. Formic acid is the most aggressive of
all organic acids containing only one carboxyl group. This
fact and the singular properties of the molecule require
that thorough testing of materials be conducted in any
medium known to contain the acid.
Comments regarding corrosion by formic acid were
introduced in the section on acetic acid, inasmuch as many
commerical processes today for producing acetic acid also
contain formic acid. A review of Tables 11, IV and XXI,
among others, will show the more aggressive character of
process streams containing formic acid. In general, the
same materials of construction suitable for handling acetic
acid can be used for the higher concentrations of formic
acid. The corrosion of a specific alloy will be slightly
greater when exposed to formic acid at the same temperature.
The major area for concern relates to concentrations of
aqueous formic acid between 50 and 90 per cent. In this
zone, the corrosion rate for Type 316 stainless steel varies
greatly and can be higher than desirable for commercial
applications. The variable test data reported probably
relate to the period of passivity of the stainless steel during
the test, because the presence of the water would tend to
extend the life of passive films on the alloy surface. Some
of the more consistent laboratory data, which agree well
with field experience, are shown in Table XXXIII. Note
the aggressive attack on the Type 316 stainless steel until
formic acid concentrations of about 90 per cent are
encountered. High rates of attack are experienced where

drippage of a formic acid-water azeotrope impinges on the


metal surface.
Table XXXIV compares the corrosion of Type 316
stainless steel with a number of other alloys in a closely
controlled laboratory test. Some anomalies are apparent,
but in general the data reflect corrosion rates to be
expected in equipment handling boiling formic acid of the
concentrations shown. As in the case of acetic acid, copper
and the cupro-nickel alloys are useful for such service in
the absence of oxygen or other oxidants. The addition of
nickel to the copper makes the resulting alloy somewhat
less sensitive to the presence of oxidants.
Data for a much wider range of alloys in aerated and
unaerated acid are provided in Table XXXV The presence
of air in the test medium has the effect anticipated by
decreasing the rate of attack on those alloys forming
protective oxide films and increasing the corrosion of
copper alloys, nickel and MONEL alloy 400. Note that
alloying a stainless steel with higher amounts of chromium
and nickel does not improve the resistance of the alloy
(Type 310 vs. Type 304 stainless steels), but the addition
of molybdenum produces a much more corrosion resistant
alloy (Types 316 and 317 stainless steels).
The data of Table XXXV also provide an interesting
illustration of the importance of testing techniques in
providing meaningful information. For example, the majority of corrosion rates for specimens of Types 316 and
317 stainless steels and CARPENTER alloy 20 show
greater attack in the vapor exposure than when the
specimens were fully immersed. This phenomenon would
be unrecognized if only the usual immersion test were
used. Yet a distillation column will have both liquid and
vapor exposures which must be analyzed before selecting
a material of construction, and the data obtained from the
vapor exposures in these tests suggest further avenues of
exploration before making a final decision.

TABLE XXXIII
Corrosion of Type 316 Stainless Steel in
Boiling Formic Acid Solutions
Test Conditions: Specimens exposed in liquid of boiling,
aqueous formic acid solutions under anaerobic conditions for 72 hours.
Corrosion Rate
Liquid

Vapor

Condensate*

Concentration of
Formic Acid, %

mm/y

mpy

mm/y

mpy

mm/y

mpy

50
70
78
90
97
100

.38
.33
.36
.15
.15
.11

15
13
14
6
6
4

.41
.48
.51
.46
.13
.08

16
19
20
18
5
3

.46
.89
.38
.61
.25
.25

18
35
15
24
10
10

*Condesate falling on one side of vapor area specimen.

Page 31

TABLE XXXIV
Corrosion of Five Alloys in Boiling Aqueous
Formic Acid Solutions
Test Conditions: Average rate of duplicate specimens exposed in boiling 100-107 C (212-223 F)
solutions for 96 hours except as noted.
No aeration or deaeration.
Corrosion Rate
Type 304
Stainless Steel
Test A
Test B*

Formic Acid

Type 316
Stainless Steel
Test A
Test B*

mm/y

mm/y

mpy

mm/y

mpy

mm/y

.18
.79
1.34
1.93
3.45
4.24**
3.45**
4.04**
4.29**
3.28**

1
5
10
20
40
50
60
70
80
90

mpy
7
31
53
76
136
167**
136**
159**
169**
129**

.36
1.07
1.52
1.75
2.39
2.11
2.11
2.31
2.13
2.11

14
42
60
69
94
83
83
91
84
83

.08
.05
25
.28
.10
.51**
.46**
.48**
.48**
.28**

3
2
10
11
4
20**
18**
19**
19**
11**

<.03
.20
.20
.20
.25
.28
.23
.25
.25
.28

C70600
(90-10
Cupro-Nickel)

Copper

mpy

Titanium

mm/y

mpy

mm/y

mpy

mm/y

.03
.03
.03
.20
.12
.25
.05
.76
.20
.23

1
1
1
8
5
10
2
30
8
9

.03
03
.03
41
.33
.53
.03
.71
13
.18

1
1
1
16
13
21
1
28
5
7

13
2.41

3.05

<.03

<1
8
8
8
10
11
9
10
10
11

mpy

5
95

120

<1

*Test solution changed each 24 hours of the 96-hour test.


**Test discontinued after 48 hours because of concentration of corrosion salts in solution.

TABLE XXXV
Corrosion of Alloys in Boiling Formic Acid Solutions
Test Conditions: Laboratory test results averaged from three separate 48-hour test periods in most cases.
Tests conducted with and without aeration in acid concentrations noted.
Corrosion Rate
10%

50%

Unaerated*
Liquid
Alloy

90%

Unaerated*

Vapor

Liquid

Aerated

Vapor

Liquid

99%

Unaerated*
Vapor

Liquid

Aerated

Vapor

Liquid

Unaerated
Vapor

Liquid

Vapor

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

Mild steel

24.13

950

Type 430
stainless steel
Type 304
stainless steel
Type 310
stainless steel
Type 316
stainless steel
Type 317
stainless steel
CARPENTER
alloy 20
HASTELLOY
alloy C
HASTELLOY
alloy B
INCONEL
alloy 600
MONEL
alloy 400
Nickel 200

11.26

444

.89

35

10.41

410

1.52

60

Copper

mpy

10.21

402

.61

24

.18

.23

.23

.53

21

<.03

<1

74

29

.36

14

.18

< 03

<1

.79

31

.13

.10

.13

.13

<.03

<1

30

12

.05

03

<1

.66

26

.10

03

.05

10

<.03

<1

.51

20

10

.08

08

.03

.76

30

.64

25

1.24

45

.20

<.03

<.1

.08

.23

.08

.03

.03

7.62

300

.23

.15

.15

.36

14

.43

17

.84

33

2.24

88

.61

24

.28

11

69

27

.41

16

.08

.18

.13

.28

11

.25

10

.15

14.30

563

37.80

93

EVERDUR 1010

.18

.23

3.30

130

.69

27

Aluminum 3003

31.09

1224

21.89

862

31.70

1248

10.16

400

7.62

300

10

<.03

<1

Titanium

.13

2.92

115

<.03

<1

Chromium
carbide with 12%
nickel binder

.51

20

*Boiling solution without sparging of any gas.

Page 32

Table XXXVI demonstrates the excellent corrosion


resistance of HASTELLOY alloy C-276 in formic acid
solutions. Throughout the entire range of temperatures
and concentrations of formic acid, the nickel-base molybdenum-chromium-iron alloy exhibits good stability.
However, in formic acid exposures, more than in acetic
acid exposures, the HASTELLOY alloys B and B-2
materials must be given consideration as materials of
construction. Other nickel and cobalt-base alloys can be
useful for specific field applications when the metallurgical properties of these alloys are required.
Applications involving heating are more demanding
than isothermal exposures for an alloy. (See comments in
the section on Acetic AcidEffect of Temperature.)
Calandria or vaporizer tubes require construction with a
corrosion-resistant alloy. Table XXXVII provides data
for six alloys tested under heat transfer conditions. The
rate of attack on the austenitic stainless steel alloys
increases sharply with a higher metal temperature under
heat transfer conditions. CARPENTER alloy 20Cb-3 and
HASTELLOY alloy B show rates of attack sufficiently
low to warrant their selection under most of these
conditions. Unfortunately, data for HASTELLOY alloy
C-276 and INCONEL alloy 625 are not included, but
they would be expected to be as good or better than that
shown for the B alloy.
Many commercial applications require the use of the

alloys at temperatures above those obtained at one atmosphere of pressure. Consequently, the effect of
increasing the temperature on the corrosion rate of the
common alloys must be determined. Table XXXVIII
presents a composite of the data contained in the report
of Miller and Wachter on corrosion by acids at high
24
temperatures. Of greatest interest is the information for
the Type 316 stainless steel. The rates are higher for this
alloy than would be expected for a test of longer
duration. The important inference to be made is that the
rate of attack approximately doubles for each 15C
(27F) increase in temperature. (It should be recognized
that this is a very rough approximation that does not
always hold true.) Corrosion tests in many other media
show a similar relationship rather than one conforming to
the ideal Arrhenius equation.
Figure 5 and isocorrosion charts (Figures 6 through
25
11), originally published by the NACE, indicate the
corrosion behavior of several alloys in formic acid.
Isocorrosion charts are intended only as guides; there are
conditions where higher or lower rates can prevail. In
fact, Figure 5 shows much lower rates for Type 316
stainless steel in boiling formic acid than is shown in the
isocorrosion chart, Figure 6. It is believed that Figure 5 is
more representative of pure formic acid and that the
higher rates shown by the isocorrosion chart must reflect
the presence of unidentified impurities.

TABLE XXXVI
Corrosion of HASTELLOYS and Related Alloys
in Formic Acid Solutions
Laboratory data obtained without aeration or deaeration using five 24-hour test periods.
(Courtesy of the Cabot Corporation, Stellite Division.)
Corrosion Rate
%
Formic Acid

Temperature
C
F

HASTELLOY
alloy B

HASTELLOY
alloy C-276

HAYNES
alloy No. 25

MULTIMET
alloy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

10

26
66
Boiling

78.8
150

.03
.23
.08

1
9
3

<.03
<.03
.13

<1
<1
5

Nil
Nil
.20

Nil
Nil
8

Nil
Nil
.10

Nil
Nil
4

20

26
66
Boiling

78.8
150

.05
.25
.10

2
10
4

< .03
<.03
.18

<1
<1
7

<.03
<.03
.25

<1
<1
10

<.03
<.03
.15

<1
<1
6

30

26
66
Boiling

78.8
150

08
.30
.08

3
12
3

<.03
<.03
.20

<1
<1
8

40

26
66
Boiling

78.8
150

.08
.28
.05

3
11
2

<.03
<.03
.13

<1
<1
5

<.03
Nil
.38

<1
Nil
15

<.03
Nil
.20

<1
Nil
8

60

26
66
Boiling

78.8
150

.05
.25
.03

2
10
1

< .03
<.03
.18

<1
<1
7

<.03
Nil
.51

<1
Nil
20

<.03
<.03
.15

<1
<1
6

90

26
66
Boiling

78.8
150

<.03
.03
<.03

<1
1
<1

<.03
<.03
.05

<1
<1
2

<.03
<.03
.15

<1
<1
6

Nil
Nil
.08

Nil
Nil
3

Page 33

Process facilities for handling formic acid are normally


constructed of Type 316L stainless steel, copper, or the
cupro-nickels. Data obtained by the exposure of alloys in a
formic acid distillation column are shown in Table XXVIII.
Other data generated by the testing of alloys in a 90%
formic acid still are contained in the reference NACE
25
report. Depending on the acid concentration, the type of

contaminants present in the acid, the temperature of the


system and the type of cooling water used, it is not unique
to find a distillation column and accessories to be constructed of a combination of Type 316L stainless steel,
C70600 (90-10 cupro-nickel), ACI CN-7M castings and
HASTELLOY alloy C-276. Other materials combinations
are obviously possible from a perusual of the data, but

TABLE XXXVII
Corrosion by Formic Acid Under Heat Transfer Conditions
Temperature
Formic Acid
Test Medium

Without
Heat Transfer

Corrosion Rate

With Heat
Transfer*

Type 304
Stainless Steel

C
10% aqueous

50% aqueous

89% aqueous

mm/y

mpy

101

103

103

214

217

217

110
125
140

110
125
140

110
125
140

230
257
284

230
257
284

230
257
284

18.85
>25.4
14.48
14.48
>25.4
>25.4
>25.4
>25.4
18.19
13.72
12.7
13.21

Type 316
Stainless Steel

742
>1000
570
570
>1000
>1000
>1000
>1000
716
540
500
520

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

10
16
62
73
39
58
60
84
10
48
40
48

.25
.41
1.57
1.85
.99
1.47
1.52
2.13
.25
1.22
1.02
1.22

HASTELLOY
alloy B

mpy

mm/y

CARPENTER
alloy 20Cb-3

INCONEL
alloy 600

MONEL
alloy 400

<.03
.05
.20
.69
.15
.23
.33
.31
.13
.10
.15
.25

<1
2
8
27
6
9
13
12
5
4
6
10

.25
1.27
1.42
2.03
.28
.23
.13
113
<.03
.13
.08
.18

10
50
56
80
11
9
5
5
<1
5
3
7

.89
1.85
1.68
1.52
1.55
1.93
3.30
2.92
1.02
1.27
1.93
1.42

35
73
66
60
61
76
130
115
40
50
76
56

3.38
16.26
>25.4
>25.4
2.21
1.93
1.22
2.54
.03
.56
.84
1.27

133
640
>1000
>1000
87
76
48
100
1
22
33
50

*Metal temperature.
Reference 10. See that publication for apparatus and technique used

TABLE XXXVIII
Corrosion of Alloys in Formic Acid at High Temperatures
(Tests conducted in sealed pressure tubes)
% Formic Acid
Test Period, days

1
1

2*
27

Test Temperature

4.6
1
Corrosion Rate

Alloy

mm/y

mpy

mm/y

mpy

Type 410 stainless steel


Type 430 stainless steel
Type 446 stainless steel
Type 304 stainless steel

170
170
170
150
170
170
100
150
170
200
150
170
170
170
150
170
150
170
150
170
150
150
170
170
170
170

338
338
338
302
338
338
212
302
338
392
302
338
338
338
302
338
302
338
302
338
302
302
338
338
338
338

.13
.20
.89

5
8
35

.46

.10

.05

.08

.03

.03

.03
.03

18

1
1

Type 310 stainless steel


Type 316 stainless steel

Type 317 stainless steel


HASTELLOY alloy C
HASTELLOY alloy B
INCONEL alloy 600
Nickel 200
MONEL alloy 400
C71500 (70-30 Cupro-nickel)
Copper
Silver
Aluminum 1100
DURIRON

24
1

mm/y

mpy

mm/y

mpy

16.26
10.41
.66

3.56
2.36
.58
1.52
1.83
1.68

1.60
.10
.23

3.30

2.34

.89

.20
.15
10.16
7.37

640
410
26

140
93
23
60
72
66

63
4
9

130

92

35

8
6
400
290

1.04
3.05

3.30

41
120

130

Reference 24

*Also contained 1.5% formaldehyde.

Page 34

extensive testing of the candidate alloys must be conducted


beforehand to assure an adequate economic life of the
equipment.
When appraising stream compositions for corrosion
testing or the designation of materials of construction, it is
important to understand the unstable nature of the onecarbon compounds. Formaldehyde reacts readily with
oxygen to produce the acid, and it is difficult to handle and
store the aldehyde without generating sufficient formic acid
to make a corrosive agent out of what would otherwise be a
rather innocuous compound. It is for this reason that Type
304 stainless steel is often selected as the material of
construction for formaldehyde storage tanks. Not only does
the use of the stainless steel provide a trouble-free material
of construction, but the lack of contamination of the
aldehyde maintains good color in the solution and reduces
the rate of oxidation of the product to additional acid. A
brief summary of proper formaldehyde storage is provided
by Teeple in reference 26.
Formate esters are also most unstable. The methyl ester
is often encountered in process streams, and, when any
water is present, must be considered as contributing to a
significant acidity in the medium.

FIG 7Isocorrosion Chart for Type 304 Stainless Steel in Formic Acid

FIG 8Isocorrosion Chart for Wrought 20 Type Alloy in Formic Acid

FIG 5Comparison of Types 304 and 316 Stainless Steels in


Various Concentrations of Boiling Formic Acid
FIG 9Isocorrosion Chart for HASTELLOY alloy B in Formic Acid

FIG 6Isocorrosion Chart for Type 316 Stainless Steel in Formic


Acid

FIG 10Isocorrosion Chart for HASTELLOY alloy C (C-276) in Formic


Acid

Page 35

FIG 11Isocorrosion Chart for MONEL alloy 400 in Formic Acid

B. Acrylic Acid
Acrylic acid is the most common 3-carbon acid encountered in industry. The great reactivity of this unsaturated
acid makes the material and its esters useful in the
preparation of a wide variety of resinous products used in
manufacturing plastics, paints, textiles, paper and polishes. There are probably some one billion pounds of the
esters produced in the USA today, of which 75% is ethyl
acrylate.
The significant fact about handling acrylic acid is that
temperatures are maintained as low as possible to prevent
homopolymerization of the acid. Distillation in vacuum
stills, dilution with innocuous solvents, storage of the
product at the lowest convenient temperatures and reaction
of the acid in polymerization processes at low temperatures
are common process conditions. Consequently, exposure
conditions in most acrylic acid applications are less severe
than in the saturated acid processes.
As with propionic acid, the acrylic acid can be considered as equivalent to acetic acid in aggressiveness at a
given temperature. However, the contaminants in acrylic
acid process streams can be different from those found in

This HASTELLOY alloy C-276 tube bundle is used in the reboiler in the
manufacture of acrylic monomers. It was found to be the most
economical material of construction for this severely corrosive service.
Courtesy Stellite Division, Cabot Corporation.

acetic acid streams and the contaminant may control the


corrosion rate.
Acrylic acid per se is not required as an end product in
large quantities as is the ester. Consequently, many of the
commercial processes are designed to prepare the ester
from a basic organic molecule without isolating the acrylic
acid. Regardless of the route to the final product, however,
all processes produce the acid as an intermediate with
subsequent esterification.
Acrylic aid, or the acid-ester in one sequence, has been
produced by at least nine different processes. Three basic
27
reactions have been used predominantly. These are the
acetylene-carbon monoxide, the nitrile and the propylene
oxidation processes. Today, the direct oxidation of propylene to acrolein and finally to the acid in a one or twostep process is the most popular.
The acetylene-carbon monoxide process relies on the
catalytic activity of nickel carbonyl in the presence of a
strong acid (hydrochloric) to prepare the acid. Obviously,
the presence of the HCl controls the corrosive conditions
existing in the process. Even at the low reaction temperatures, 30-52 C (86-126 F), the reaction step is most
corrosive and is conducted in glass, ceramics and
TEFLON* equipment. Following this step, the nickelbase molybdenum alloys can be used, and as the mineral
acid is removed, the alloy content of the materials of
construction can be reduced until Type 316 stainless steel
is acceptable to handle the acrylic acid.
The nitrile procedure for production of the acid suffers
the same drawback from a materials standpoint with
sulfuric acid used to produce an organic sulfate which can
be released to the acid or directly reacted to form the ester.
Ammonium acid sulfate is formed as a by-product, and
the higher process temperatures, 150 C (300 F) region,
generate SO2 and SO3 which must be contended with in
equipment design. The problems encountered are essentially the same whether using acrylonitrile or ethylene
oxide and hydrogen cyanide as the starting materials.
Table XXXIX provides typical corrosion data for a
nitrile type process operation through the distillation of
the crude acid. Sets of data are given for two exposures in
the same equipment (top head of reactor condenser) to
show the wide variation in corrosion rates experienced
during different periods of operation. Such large changes
in the corrosive environment may be found wherever a
mineral acid is mixed with an organic acid. When using
metallic materials of construction in such processes, the
operation must be conducted with particular care to
maintain favorable conditions for a maximum life of the
equipment. A few hours of adverse operating conditions
can severely damage equipment under such circumstances. Monitoring of the corrosion by continuous or
sequential testing is also advised to detect periods of
unusual corrosion. This process is obviously most corrosive until the decomposition products of the inorganic
acid and salts are removed. The usual materials, primarily
the austenitic stainless steels, are then used to process the
acrylic acid.
*Trademark of E.I. duPont de Nemours & Co.

Page 36

TABLE XXXIX
Corrosion of Alloys in a Nitrile-Type Acrylic Acid Process
Corrosion Rate
Exposure*

3A

38

Alloy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

Type 304
Stainless Steel

>7.62

>300

2.24

88

10.16

> 400

.03

<.03

<1

08

03

<.03

<1

Type 316
Stainless Steel
Type 201
Stainless Steel
CARPENTER
alloy 20
INCONEL
alloy 600
INCONEL
alloy 625
HASTELLOY
alloy C
HASTELLOY
alloy B
MONEL
alloy 400
C70600 (90-10
Cupro-nickel)
Copper
Lead,
chemical
Aluminum 3003
Titanium
Zirconium
Tantalum

>7.62

>300

2.11

83

10.16

400

Nil

Nil

<.03

<1

<.03

<1

<.03

<1

<.03

<1

3.00

118

Nil

Nil

Nil

Nil

13

<.03

<1

>7.62

>300

64

25

4.98

196

Nil

Nil

<.03

<1

Nil

Nil

<.03

<1

>7.62

> 300

4.57

180

03

20

<.03

<1

.89

35

<.03

<1

7.11

280

2.95

116

74

29

<.03

<1

1.35

53

74

29

25

10

>7.62

>300

2.54

100

2.64

104

.05

03

15

.20

> 7.62

> 300

1.14

45

6.09
>7.62

240
>300

6.35

250

2.95
5.28

116
208

1.17

46

.05

05
25

2
10

23
30

9
12

76
> 5.08

30
> 200

>7.62

> 300

>7.62
.86
.03

>300
34
1

10. 16
1.35
<.03

> 400
53
<1

13
<.03
<.03

5
<1
<1

.03

38

15

33
<.03

13
<1

> 7.62

> 300

<.03

<1

*1
2
3A
3B
4
5
6
7
8

Reactor liquid for 1600 hours at ca. 125 C (257 F).


Reactor vapor line to condenser for 190 hours at ca. 130 C (266 F).
Reactor vapor condenser top head for 1200 hours at ca. 130 C (266 F).
Same as 3A during different period for 2600 hours.
Condensate from exposure No. 3 at ca. 30 C (86 F) for 190 hours.
Bottom of extractor for 1600 hours at ca. 30 C (86 F).
Top of extractor for 1600 hours at ca. 30 C (86 F).
Base of crude acid stripping still for 4000 hours at 110 C (230 F).
Overhead liquid-vapor from exposure No. 7 (feed to acrylic acid refining still) for 3 days at 88 C (190 F) (air present).

TABLE XL
Corrosion of Alloys in Propylene Oxidation
Process for Acrylic Acid
Corrosion Rate
Exposure*
Alloy
Type 304
Stainless Steel
Type 316
Stainless Steel
CARPENTER
alloy 20
HASTELLOY
alloy C
INCONEL
alloy 625
INCONEL
alloy 600
MONEL
alloy 400
Copper
Nickel 200

1
2
3
4
5
6
7
8
9
10
11
12
mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
<.03 <1
<.03
<1 <.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1
<.03
<1 <.03
<1
<.03
<1
<.03
<1 <.03 <1
<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

.25

10

.25

10

.03

.13

.48

19

.97
.28

38
11

.81
<.03

32
<1

.20
.03

8
1

.05
.05

2
2

.13

.08

.53

21

.91

36

* 1Propylene oxidation converter at 400 C (752 F) for 180 days.


2Quench line from converter at 110 C (230 F) for 300 days.
3Scrubber circulating line at 85 C (185 F) for 31 days.
4Acrolein stripper base at 140 C (284 F) for 300 days.
5Crude acrolein separator pot at 25 C (77 F) for 180 days.
6Acrolein refining still base at 105 C (221 F) for 20 days.

7Acrolein oxidation converter at 220 C (428 F) for 220 days.


8Oxidation reactor quench line at 80 C (175 F) for 220 days.
9Solvent extraction column overhead at 42 C (108 F) for 8 days.
10Water layer from solvent column separator at 35 C (95 F) for 330 days.
11Solvent recovery column base at 105 C (221 F) for 110 days.
12Recovery column for No. 10 above at 95 C (203 F) for 360 days.

Page 37

TABLE XLI
Corrosion of Stainless Steels During the Preparation
of -Methacrylic Acid
Corrosion Rate
Exposure

Type 304
Type 316
CARPENTER HASTELLOY HASTELLOY
Stainless Steel Stainless Steel
alloy 20
alloy C
alloy B
mpy

DURIRON

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

.03

.03

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

.03

.05

Nil

Nil

.51

20

<.03

<1

<.03

<1

<.03

<1

<.03

<1

.38

15

1.88

74

<.03

<1

.23

TABLE XLII
Corrosion of Alloys in Dimethyl Acrylic
(Seneceoic) Acid
Field test obtained by exposure of alloys in the
overhead stream of a refining column at 145C (293F)
for three days.
Corrosion Rate
Alloy

mm/y

mpy

Type 304 Stainless Steel


Type 316 Stainless Steel (annealed)
Type 316 Stainless Steel (sensitized)
HASTELLOY alloy C
HASTELLOY alloy B
MONEL alloy 400
Copper

1.83
.18
.18
<.03
.05
.46
1.45

72
7
7
<1
2
18
57

mpy mm/y

Aluminum
3003

mm/y
Oxidation of the acid by
air blowing of the
aldehyde at 40 C (104 F)
Distillation of the crude
oxidation product at ca.
55 C (131 F) (liquid
exposure)
As above (vapor exposure)

mm/y

Silicon
Bronze

mpy mm/y mpy

pylene-acrolein process. The oxidation product of the methacrylic aldehyde would contain some oxidized decomposition compounds such as formic and acetic acids.
However, the reasonable low temperatures at which the
product must be handled, combined with the low concentration of such contaminants, does not produce an
aggressive medium for the stainless steels. The data of
Table XLI show results obtained in oxidation and primary
distillation steps of the process.
Further information relating to the acrylic acids is
contained in Table XLII. In processing the more stable
dimethyl acrylic acid at the higher temperatures, it is
apparent that a Type 316 stainless steel is required. The
temperature of the operation exceeds the point where the
Type 304 stainless steel is adequately resistant.
C. C3 Through C8 Acids

The major commercial approach to acrylic acid production today is the direct oxidation of propylene to acrolein
with subsequent oxidation to acrylic acid or a one-step
oxidation with only the acid recovered. One advantage of
the process is the milder corrosive conditions existing
throughout the unit. Steel and the austenitic stainless
steels may be used for all equipment except where
chloride stress-corrosion cracking of the stainless steels
requires the use of Alloy 600, Alloy 400, or other crackresistant alloys. Table XL provides data regarding the
corrosion of a number of alloys in significant portions of a
propylene oxidation process. Although the austenitic
stainless steels are resistant to the primary corrosive
agents throughout the process, the use of INCONEL alloy
600 and other high alloys have been used in the process
for the reason cited.
Similar data were obtained by the exposure of alloys in
a plant preparing -methyl acrylic (crotonic, 2-buteneoic)
acid. Types 304L and 316L stainless steels and CARPENTER alloy 20Cb-3 were unattacked in process handling of
the acid up to 90 C (194 F) in a process similar to that
described for the production of acrylic acid by the pro-

The first of the remaining higher acids, the 3-carbon


propionic acid, is produced in considerable quantity. The
acid and its unsaturated counterpart, acrylic acid, are very
similar to acetic acid in reactivity with metals. The
corrosion rate of the common materials of construction is
essentially the same in propionic and acrylic acid as in
acetic acid at the same temperature. Certainly, all factors
described as influencing the corrosion of alloys in acetic
acid are applicable to corrosion mechanisms in the 3carbon acids.
Corrosion rates of various alloys in boiling propionic
5
acid solutions are shown in Figure 12. Elder points out
the anomalous results that can result from the short test
period used for these tests and the effect of dissolved
oxygen on the results. The beneficial effect of added
oxygen on austenitic stainless steels is not restricted to
laboratory tests but was also attained in the field as shown
in Table XLIII. It is interesting to note that a maximum
rate of attack on the stainless steels appears to occur at
approximately the same concentrations (60-80 per cent) as
found for acetic acid in boiling solutions. For welded
construction, the low carbon stainless steel grades should
be employed unless it has been definitely established that

Page 38

welded regular carbon grades are free from intergranular


corrosion in the heat-affected zones of welds.
To supplement the curves of Figure 12, the data of
Table XLIV summarize the resistance of several alloys to
propionic acid solutions below the boiling point.
When the temperature is raised appreciably and propionic anhydride is added to the acid, the stainless steels,
including the iron-base nickel-chromium-copper-molybdenum alloys, are no longer useful as a material of
construction. Table XLV shows data derived from a test
conducted at 260 C (500 F).
For all alloys considered for a specific service involving
propionic acid, the data presented for acetic acid may be
used as a general guide. It is important to use data
acquired at the proper temperature, keeping in mind that
the boiling point of propionic acid is much higher than
that of acetic acid and that tests conducted below the
boiling point are not the same as those made in a boiling
solution.
Organic acids of greater chain length than the 3-carbon
acids are produced in smaller quantity, but constitute an
important group of products, primarily as intermediates in
the preparation of pharmaceuticals, agricultural chemicals,
food products, plasticizers and other end-use chemicals.
The chemical characteristics of the longer monocarboxylic acids are important in interpreting the corrosive
potential of the products. Complete miscibility in water of
the two three-carbon acids (propionic and acrylic) is
achieved, but the solubility of the remaining acids decreases rapidly with increasing chain length. The extent of
dissociation of the dissolved acid remains essentially the
same as acetic acid. However, in the pure form, or in
organic dilutions of the acids, the higher acids are in-

HASTELLOY alloy C-276 replaced silver in this primary cooler for propionic
acid. The alloy was found to have better resistance to thermal cycling than the
precious metal. Courtesy of Stellite Division, Cabot Corporation.

creasingly stable with increasing chain length. Numerous


tests conducted in butyric and higher acids indicate that
the exposure is innocuous until some specific temperature
is reached, at which point sufficient dissociation is
achieved to initiate and sustain corrosion. This critical
temperature is higher for each succeeding higher homologue in the series. Thus, for a specific acid, a temperature
of 190 C (374 F) may produce essentially no corrosion
on a Type 304 stainless steel, but a temperature of 210 C
(410 F) may produce exceedingly high corrosion rates.

FIG 12Corrosion of Alloys in Propionic Acid at the Boiling Temperature

Page 39

TABLE XLIII
Effect of Oxygen on Corrosion of Stainless Steel in Propionic Acid
Conditions: 95% propionic acid containing 2% water, alcohol, ketone and higher acids
used in laboratory tests and processed in field.
Corrosion Rate
Type of Test

Additive

Temperature

Exposure

Type 316
Stainless Steel

Type 304
Stainless Steel

Type 202
Stainless Steel

mm/y

mpy

mm/y

mpy

mm/y

mpy

Laboratory

None

122
to
135

252
to
275

Liquid
Vapor
Condensate

.15
.20
.05

6
8
2

.30
.28
.36

12
11
14

Laboratory

Air Sparged

122
to
135

252
to
275

Liquid
Vapor
Condensate

Nil
Nil
Nil

Nil
Nil
Nil

1.63
.15
Nil

64
6
01

Laboratory

9 ppm H 2 0 2

122
to
135

252
to
275

Liquid
Vapor
Condensate

01
01
Nil

0.3
0.2
0.1

.04
.02
Nil

1.5
0.6
0.1

Laboratory

1 ppm H 2 O 2 +
air sparged

122
to
135

252
to
275

Liquid
Vapor
Condensate

Nil
Nil
Nil

Nil
Nil
Nil

Nil
Nil
Nil

Nil
Nil
Nil

Laboratory

200 PPM CuSO 4

122
to
135

252
to
275

Liquid
Vapor
Condensate

Nil
Nil
Nil

<0.1
<0.1
<0.1

Nil
Nil
Nil

<0.1
<0.1
<0.1

Air and H 2 O 2
injected
in feed stream

110
to
137

230
to
279

Kettle
Based on column
Feed line
Middle of column
Top of column

Nil
Nil
Nil
Nil
Nil

<0.1
<0.1-0.1
0.1
0.1
<0.1

Nil
Nil
Nil
Nii
Nil

<0.1
<0.1-0.1
0.1
<0.1
<0.1

Field Column
processing the acid*

Nil
Nil-.03
Nil
Nil
01

<0.1
<0.1-1
0.1
0.1
0.3

*Three separate field exposures made of 168-254 hours.

Table XLVI shows data generated by the laboratory


immersion test of five alloys in C2 through C10 acids. The
difficulty with such laboratory tests relates to the exposure
of the copper alloys and the stainless steels. Organic acids
are excellent retainers of air in solution. Heating of the
acid at temperatures below the boiling point does not
expel all the oxygen, and corrosion rates on the copper
alloys will be higher than would be experienced in a closed
system devoid of oxygen. On the other hand, the stainless
steels retain passivity for a longer time in such media
before corrosion is initiated. Longer test periods, dynamic
test apparatus and a close control of the entire environment are important when attempting to identify specific
materials of construction for a proposed application.
However, the data of this table are consistent with field
experience. As indicated by the laboratory tests, Types
316 and 316L stainless steels have excellent resistance to
the acids to temperatures approaching the boiling point at
atmospheric pressure. For this reason, the approximate
boiling point temperature of each acid is listed in the table.
The more extensive listing of alloys exposed in four, six
and eight-carbon acids is given in Tables XLVII and
XLVIII. The essential resistance of Type 316 stainless
steel in organic acids is maintained in these higher acids

whether the acid is refined or contaminated with the lower


acids (crude). The higher iron or nickel-base alloys
containing chromium and molybdenum exhibit the same
excellent stability in the higher acids as noted in the one
and two-carbon compounds.
Corrosion to be anticipated in a more modern process
for the preparation of the longer acids is indicated in Table
XLIX. Here, the catalyzed oxidation of a straight-chain
hydrocarbon to an eight-carbon acid produced no significant corrosion of the stainless steels. Although only .13
mm/y (5 mpy) corrosion of Type 304 stainless steel was
obtained in this instance, the choice of Types 316 or 316L
stainless steels for such a reactor would be advisable to
assure adequate resistance to variations in process conditions that might occur.
When working with the higher organic acids, it is
difficult to provide test conditions and a length of exposure sufficient to produce intergranular attack on sensitized stainless steel. The higher acids will produce
selective attack on a structure containing carbide precipitation, however, and the use of the L-grade or stabilized stainless steels at temperatures above 100 C
(212 F) is suggested as a safeguard, regardless of the test
data obtained.

Page 40

Combinations of sulfuric acid and the organic acids are


often found in the process industry. The mineral acid is
added to catalyze certain reactions with the organic acid or
to react with unwanted impurities in the acid. The effect of
adding one or two per cent of strong sulfuric acid to an
eight-carbon organic acid is shown in Table L. Under these
conditions, Type 304 stainless steel was as resistant as the
Type 316 alloy in the temperature regions explored. The
anamolous data of test 4 suggest that the stability of the
stainless steels may be borderline under these conditions,
although even higher temperatures failed to destroy the
passivity of the alloys. The strong oxidizing capacity of the
concentrated sulfuric acid probably aids in maintaining

passivity of the stainless steels in this medium. As


discussed in the section on acetic acid, the use of a heating
coil in such an environment would pose a different
problem. Under heat-flux conditions, it is unlikely that
the 300 series stainless steels would show adequate
resistance to such a mixture. Also, if a water wash of the
organic acid is to be made to remove the sulfuric acid, the
aqueous phase containing a dilute mineral acid could be
extremely aggressive to the 300 series alloys. Higher alloys
of the 20 type for wrought materials or the CN-7M
castings would be minimal for resistance to the diluted
mineral acid in the presence of the organic acid.

TABLE XLIV
Corrosion of Stainless Steels in Propionic Acid
Below the Boiling Temperature
Conditions: Duplicate tests in various concentrations of
propionic acid at 75 and 50 C (167 and 122 F)
without aeration or deaeration.
Corrosion Rate
% Propionic
Acid

Type 420
Stainless Steel
75 C (167 F)

Type 304
Stainless Steel

50 C (122 F)

mm/y
99
80
67
50
33
20

mpy

mm/y

mpy

2.54
52.32
90.93
79.76
39.88
42.67

100
2060
3580
3140
1570
1680

.03
6.09
9.27
1.65
4.83
1.57

1
240
365
65
190
62

75 C (167 F)
mm/y
Nil
.05
.03
<.03
<.03
<.03

mpy
Nil
2
1
<1
<1
<1

Type 316
Stainless Steel

50 C (122 F)

75 C (167 F)

50 C (122 F)

mm/y

mpy

mm/y

mpy

mm/y

mpy

Nil
.05
.05
<.03
Nil
Nil

Nil
2
2
<1
Nil
Nil

Nil
<.03
Nil
Nil
<.03
<.03

Nil
<1
Nil
Nil
<1
<1

Nil
.03
Nil
<.03
<.03
Nil

Nil
1
Nil
<1
<1
Nil

Corrosion Rate
% Proponic
Acid

Type 318
Stainless Steel
75 C (167 F)
mm/y

99
80
67
50
33
20

<.03
<.03
Nil
Nil
<.03
<.03

HASTELLOY
alloy C

50 C (122 F)

mpy

mm/y

<1
<1
Nil
Nil
<1
<1

Nil
.03
Nil
Nil
Nil
Nil

75 C (167 F)

mpy

mm/y

mpy

Nil
1
Nil
Nil
Nil
Nil

Nil
Nil
.03
<.03
Nil
Nil

HASTELLOY
alloy B

50 C (122 F)
mm/y

Nil
Nil
1
<1
Nil
Nil

Nil
Nil
Nil
Nil
Nil
Nil

mpy
Nil
Nil
Nil
Nil
Nil
Nil

75 C (167 F)

50 C (122 F)

mm/y

mpy

mm/y

mpy

.64
.30
.28
.10
.08
.05

25
12
11
4
3
2

.15
.61
.30
.38
.20
<.03

6
24
12
15
8
<1

Corrosion Rate
% Propionic
Acid

INCONEL
alloy 600
75 C (167 F)
mm/y

99
80
67
50
33
20

.38
.48
.18
.10
.10
.13

MONEL
alloy 400

50 C (122 F)

75 C (167 F)

mpy

mm/y

mpy

mm/y

mpy

15
19
7
4
4
5

<.03
.41
.36
.20
.18
.13

<1
16
14
8
7
5

1.19
.15
.13
.13
.10
.13

47
6
5
5
4
5

Page 41

Copper

50 C (122 F)
mm/y
.48
.41
.23
.28
.05
.18

mpy
19
16
9
11
2
7

75 C (167 F)
mm/y
>1.27
.23
.28
.25
.28
.05

mpy
>50
9
11
10
11
2

50 C (122 F)
mm/y

mpy

1.02
1.09
.41
.38
<.03
.13

40
43
16
15
<1
5

TABLE XLV

TABLE XLVII

Corrosion of Stainless Steel in a Propionic


Acid-Anhydride Mixture

Corrosion of Proprietary Alloys in 2-Ethyl Butyric Acid

Conditions: Specimens exposed in pressure equipment


at 260 C (500 F) and 300 atmospheres
pressure from 4 to 7-hour periods in a 65%
propionic acid/35%propionic anhydride
mixture with continuous feed of two liters/
hour.
Corrosion Rate
Alloy

Liquid

mm/y
Type 430 Stainless Steel
129.41
Type 304 Stainless Steel
141.86
Type 347 Stainless Steel
3.63
Type 316 Stainless Steel
9.91
Type 316 Stainless Steel (Sen.)
12.01
Type 317 Stainless Steel
4.55
Type 318 Stainless Steel
7.95
CARPENTER alloy 20
7.26

Vapor

mpy
5095
5585
143
390
475
179
313
286

mm/y
80,01
78.10
116.84
7,09
4.01
2.44
7.65
8.36

mpy
3150
3075
4600
279
158
96
301
329

Duplicate specimens exposed for 48 hours or longer in


refined boiling acid without aeration or deaeration.

Corrosion Rate
Alloy

mm/y

Type 316 Stainless Steel


CRUCIBLE alloy 223
Titanium
WAUKESHA 23
WAUKESHA 54
WAUKESHA 88
KROMARC 55
E-BRITE 26-1
CRUCIBLE 26-1
CROLOY 16-1
CARPENTER alloy 20Cb-3

mpy

.03
.05
<.03
.89
.18
.28
.03
<.03
.03
5.33
<.03

1
2
<1
35
7
11
1
<1
1
210
<1

TABLE XLVI
Corrosion of Alloys in Higher Organic Acids
Conditions: Laboratory tests for 48 hours at temperatures
shown in refined (99.9+) acids.
Corrosion Rate
Acid (Approximate
boiling point)

Test
Carbon Steel
Temperature
C

26
116
26
Propionic (140 C or 284 F)
110
26
Butyric (163 C or 325 F)
163
26
Valeric (185 C or 365 F)
140
26
2-Ethylbutyric (190 C or 374 F)
150
2-Methylpentanoic
26
(195 C or 383 F)
150
2-Ethylhexanoic
26
(220 C or 428 F)
190
26
Iso-octanoic (240 C or 464 F)
190
26
Iso-decanoic (265 C or 509 F)
190
Acetic (116 C or 240 F)

Copper
mpy

Silicon
Bronze

Type 304
Type 316
Stainless Steel Stainless Steel

mm/y

mpy

mm/y

mm/y

mpy

mm/y

78.8
240
78.8
240
78.8
325
78.8
284
78.8
302

2.79
5.33
.71
1.98
.15

.05
1.37
.18
.86

110
210
28
78
6

2
54
7
34

.28
.08
.05
2.13
Nil

.05
2.06
.03
.41

11
3
3
84
Nil

2
27
1
16

.41
.08
.15
3.40
.05

.05
.13
.03
.23

16
3
6
134
2

2
5
1
9

<.03
.25
<.03
.13
<.03
1.14
<.03
<.03
<.03
.53

mpy
<1
10
<1
5
<1
45
<1
<1
<1
21

<.03
.08
<.03
<.03
<.03
.10
<.03
<.03
<.03
<.03

mm/y

mpy
<1
3
<1
<1
<1
4
<1
<1
<1
<1

78.8
302

.03
.53

1
21

.08
.30

3
12

.10
.08

4
3

<.03
<.03

<1
<1

<.03
<.03

<1
<1

78.8
374
78.8
374
78.8
374

.03
1.27
.03
.89
.03
.84

1
50
1
35
<1
33

<.03
<.03
05
<.03
<.03
<.03

<1
<1
2
<1
<1
<1

<.03
<.03
.03
<.03
<.03
<.03

<1
<1
1
<1
<1
<1

<.03
.20
<.03
.43
<.03
.20

<1
8
<1
17
<1
8

<.03
<.03
<.03
<.03
<.03
<.03

<1
<1
<1
<1
<1
<1

Reference 5

Page 42

TABLE XLVIII
Corrosion of Alloys in Higher Organic Acids
(Laboratory Tests)
Corrosion Rate

Temp.
Acid
2- Ethyl butyric acid
Crude acid (60%)
Crude acid
Refined acid
2- Ethyl hexanoic acid
Refined acid
Refined acid
n- Butyric acid
+5% Acetic Acid
agitated

Type 304
Stainless
Steel

Time

days mm/y

26
115
125

78.8
239
257

10
10
1

125
150
130

257
302
266

1
5
60

Type 316
Stainless
Steel

CARPENTER

INCOLOY

HASTELLOY

alloy 20

alloy 825

alloy C

mpy mm/y mpy

mm/y mpy

mm/y

Copper

mpy

mm/y

mpy mm/y

Nil
.08
Nil

Nil
3
Nil

Nil
.08
Nil

Nil
3
Nil

Nil
61

Nil
24

<.03
05

<1
2

.03

.03

.01

0.3

Steel

mpy

mm/y

mpy

<.03
1.52

<1
60

.89

35

TABLE XLIX
Corrosion of Alloys During Preparation
of n-Octanoic Acid
Corrosion Rate

Temp.

Type 304
Stainless
Steel

Time

Type 316
Stainless
Steel

CARPENTER

HASTELLOY

alloy 20

alloy C

Exposure

days

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

Preparation of the
acid by carbonylation
of the appropriate
olefin

175

347

13

<.03

<1

<.03

<1

<.03

<1

Distillation of the
octanoic acid from
above preparation

230

446

2.54

100

<.03

<1

<.03

<1

<.03

<1

TABLE L
Corrosion of Alloys in 2-Ethyl Hexanoic Acid
Corrosion Rate
Test No.

Alloy

mm/y

Type 304 Stainless Steel


Type 316 Stainless Steel
CARPENTER alloy 20
HASTELLOY alloy C
HASTELLOY alloy B
Silicon Bronze
Copper

08
.15
.10
.03
<.03
05
15

2
mpy

mm/y

3
6
4
1
<1
2
6

05
13
.05
<.03
<.03
05
.15

3
mpy
2
5
2
<1
<1
2
6

mm/y

mpy

mm/y

08
08

.20
1.12

3
3

8
44

36
46
.08
.05
<.03
.18
.18

5
mpy
14
18
3
2
<1
7
7

mm/y
05
15
.08
.03
.03
08
.23

6
mpy
2
6
3
1
1
3
9

mm/y

mpy

.08
13

56
.66

3
5

22
26

a Test 11% of 98% H SO added to commercial grade 2-ethyl hexanoic acid. Solution at 90 C (194 F) at atmospheric pressure for
2
4
7 days with agitation.
Test 21% of 98% H 2 SO 4 added as before. Solution at 120 C (248 F) at atmospheric pressure for 7 days with agitation.
Test 31% of 98% H 2 SO 4 added as before. Solution averaged 143 C (290 F) at 200 mm pressure for 3 days with agitation.
Test 4Same as Test 1 except 2% H 2 SO 4 added.
Test 5Same as Test 2 except 2% H 2 SO 4 added.
Test 62% H 2 SO 4 added; average temperature of 142 C (288 F) at 300 mm pressure for 3 days.

Page 43

D. Fatty Acids
The fatty acids comprise those organic acids exceeding
four carbons in length according to some chemical text
definitions. However, the term as used industrially and in
this text refers to the higher acids of six or more carbons.
These are characterized by lauric, oleic, linoleic, stearic,
tall oil and rosin acids as produced for commerical use
from products of the meat, agricultural and paper industry.
The large volume product of industry is not a pure
compound, but a mixture of two or more of the compounds meeting certain chemical specifications.
At the lower temperatures, the acids may be considered
as harmless polar oils. However, when the products are
heated to the high temperatures necessary for processing
and production, significant corrosion of steel can result.
Fortunately, there is a wide variety of alloys which have
excellent resistance to the conditions of production and
subsequent use of the acids. A proper economic analysis
of the use of the alternative materials is necessary to
achieve an optimum selection.

Data reported for the corrosion of metals in the fatty


acids are not explicit regarding stream compositons. As a
consequence, a comparison of the results obtained in a
number of industrial exposures at various temperatures is
necessary to gain a proper view of corrosion to be
expected in these media. A number of factors can
influence the corrosion rates observed:
Light ends (lower acids), if allowed to remain in the
mixed fatty acids, can result in a more aggressive
environment.
The ratio of fatty to rosin acids affects the corrosion rate.
The presence or absence of water will have an effect,
particularly on the corrosion of the stainless steels.
Decomposition products generated by overheating the
acids will add to the corrosiveness of the solution.
Pretreatment of the acids may leave traces of ions in the
acids that increase corrosivity.
The temperature of the processing operation is a major
variable of concern.

TABLE LI
Corrosion of Alloys in Tall Oil Fractions
Corrosion Rate
Conditionsa

Temperature C (F)
Time, days
Exposure

100(212)
30
Vapor

Alloy

275(527)
195
Liquid

Vapor

mpy

mpy

10

11

12

13

14

15

25(77)
19
Liquid

265(509)
54
Liquid

265(509)
134
Liquid

265(509)
100
Liquid

220(128)
242
Vapor

250(482)
66
LiqVap.

240(464)
50
LiqVap.

265(509)
73
Liquid

247(477)
66
Vapor

247(477)
66
LiqVap.

220(428)
66
Vapor

260(500)
63
Vapor

mpy

.09
.06

3.4
2.5

.02
.02
.03
Nil

0.9
07
1
0.1

.77
.38
.20
.25

30
15
8
10

.25
.08
.09
.09

Nil*

01

>.76

>30

>7.6

Nil

0.1

.36

14

<.03

<1

.05

Nil

0.1

>.76

>30

>7.6

Nil

0.1

>.76

>30

.46

Nil

0.1

<.03

<1

.08

>7.6

>30

Consumed
>6.35 >250

mm/y

mm/y

Steel
Cast Iron
NiResist
Type 2
Nickel 200
MONEL alloy 400
INCONEL alloy 600
Type 304
Stainless Steel
Type 316
Stainless Steel
Type 31 7
Stainless Steel
CG8M Casting
Type 310
Stainless Steel
Type 330
Stainless Steel
INCOLOY alloy 825
INCOLOY alloy 800
INCOLOY alloy 804
HASTELLOY
alloy C
HASTELLOY
alloy B
Copper
CN7M Casting
Titanium

mm/y

300(572)
3
Liquid

260(500)

mm/y

Consumed

>6.35 >250 11.1

mpy

mm/y

mpy

mm/y

mpy

mpy

Consumed

mm/y

mpy

.43

17

mpy

mm/y

mpy

.15
.28

6
11

.43

17

.79

31

.91
1.60

36
83

.43*

17

.61*

24*

.15

.79

31

3*

.03*

.10

Nil

Nil

Nil

Nil

Nil

.02

0.8

Nil

Nil

Nil

NII

Nil

Nil

Nil

Nil

Nil

Nil

Nil

0.3
_
41

Nil
Nil

Nil
Nil

Nil*

NII

.08

Nil

Nil

mpy

mm/y

mpy

mm/y

mm/y

.13
.20
.05

5
8
2

0.9
0.1
0.1

3.5
0.5
0.2

.17

6.6

.23

>30 1.57

62

Nil

0.1

4.70

185

Consumed

Nil

0.1

.86

34

.84

33

.20

.08

3I

.05

1.78*

70

08*

Nil

NII

.23

.08
.10

3
4

.03

Nil
Nil

Nil
0.1

Nil

0.1

.99*

39

Nil

>30

.15

18

.05

Nil

NII

.02
2.67
86

0.7
105
34

.61*
>2.13
>2.29

24*
>84
>90

<.03

<1

.03

Nil

Nil

Nil

Nil

Nil

Nil

.01

.05

Nil

>7.6

> 30

.25

10

Nil

Nil

.01

Nil

Nil

.71

28

.03
Nil

1
Nil

Nil
Nil

Nil
Nil

.02

.06

1.04

*Pitted

aConditions

mm/y

10
31
3.6
3.7

Consumed

mm/y

440

mpy

References 30, 31, 49. 52

of the exposures:

1 Field test in vapor of light-odor tall oil fraction during distillation in vacuum column. Water present.
2 Field test in bottom and top of tall oil vacuum distillation column. Oil (presumably crude) from southern kraft pulp mill.
3 Laboratory test in crude tall oil acids from kraft pulp mill distilled under vacuum with agitation of 300 rpm in kettle.52
4 Laboratory test in crude and semi-refined oil with velocity of 0.3 fps provided in liquid.
5 Field test in base of tall oil distillation column (20% oleic acids, 60% rosin acids and 20% pitch).30
6 Field test in base of tall oil distillation column (65% fatty acids and 35% rosin acids).30
7 Field distillation of 65% fatty acid35 % rosin acids. 31
8 Field distillation of 93% fatty acids5% rosin acids.31
9 Field distillation of 90-93% oleic acids with <1% rosin acids with steam injected. Velocity of 62 fps.31
10 Field test six inches above the outlet of a reboiler on 97% fatty acids,1.5% rosin acids and 1.7% residues with high velocity.31
11 Field test in heat exchanger head handling 85% fatty acids and 15% rosin acids with steam present.
12 Field test in reboiler nozzle at base of distillation column handling 90-93% oleic acids and 1% rosin acids with steam injected.
13 Field test on distillation column tray near bottom while processing 90% oleic acids, 2% stearic acid, 0.4% rosin acids, 0.5 light ends and 6.4% higher
acids with steam present.
14 Field test in top of distillation column handling analysis of No. 13 above.
15 Field test near bottom of distillation column handling 30-32% rosin acids, 8-20% oleic acids and 62-48% higher boiling acids with steam present.

Page 44

mm/y

mpy

mm/y

mpy

mm/y

mpy

Pitting and crevice corrosion can occur on essentially


all alloys in these environments and must be appraised
before a material is selected. Extensive comments on the
processing of the fatty acids and the selection of materials
of construction are contained in references 28-34.
One of the most important sources of fatty acids today
is the pulp and paper industry where tall oil fractions are
recovered and refined. These are composed of the
straight-chain fatty acids and mixed rosin acids. Table LI
shows results compiled from various sources. Whenever
possible, the stream compositions have been defined.

TABLE LII
Effect of Temperature on Corrosion in Refined Tall Oil
Conditions: Laboratory tests conducted in liquid of
same oil at various temperatures.
Corrosion Rate
285 C (545 F) 300 C (572 F) 315 C (599 F) 330 C (626 F)
Material

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

Type 302

4.57

180

12.7

500

20.32

800

Type 316

.10

.10

1.35

53

12.7

500

Stainless Steel
Type 317

.03

.03

.53

21

.28

11

Stainless Steel

Stainless Steel
HASTELLOY alloy C

.10

.13

.10

INCONEL alloy 600

.25

10

.25

1 0

.33

13

Note that Types 316 and 316L stainless steels are useful
for many tall oil processing requirements but, in some
instances, either an excess of light ends or an exceptionally high temperature causes high rates with this alloy.
In these cases, the use of Types 317 or 317L stainless
steels or alloys with a higher molybdenum content should
be investigated in the search for an economical material of
construction. If these alloys are inadequate, the use of
more highly alloyed materials can be considered. The
nickel-base molybdenum-chromium-iron alloys show essentially a nil corrosion rate in all such exposures.
Alloy 600 is a contender for use in a number of applications and should not be overlooked. The use of nickelcopper alloys or copper-nickel alloys varies depending on
the oxidizing capacity of the solution, as would be
expected. In the absence of oxidants, the rate of attack on
these alloys is acceptably low.
It has been stated that streams containing a higher
proportion of the straight chain fatty acid produced more
corrosion than those containing a higher ratio of rosin
(cyclic) acids. This does not appear to be invariably true.
The presence or absence of steam has a significant
effect on the corrosion to be expected, particularly as
observed for the stainless steels. The oxidizing capacity of
the water reduces corrosion rates on the stainless steels
appreciably while accentuating attack on the nickel-copper
and/or copper-base alloys.
As with any other corrosive environment, the effect of
temperature must be carefully defined. Table LII shows
data for five alloys exposed to the same refined tall oil

TABLE Llll
Corrosion of Metals in Vegetable Fatty Acids
Conditionsa
Temp. C (F)
Time, days
Exposure

1
370 (698)
45
Liq-vap.

2
370 (698)
3
Vapor

3
190 (374)
30
Liquid

4
190 (374)
23
Liq-vap.

5
277 (530)
50
Vapor

6
116(240)
32
Vapor

7
255(491)
42
Vapor

Corrosion Rate
Alloy

mm/y

Carbon Steel
Cast Iron
Ni-Resist Type 2
Type 304 Stainless Steel
Type 309 Stainless Steel
Type 316 Stainless Steel
Type 317 Stainless Steel
INCONEL alloy 600
Nickel 200
MONEL alloy 400
C71500 (70-30 Cupro-nickel)
HASTELLOY alloy C

mpy

01

Nil

Nil
08
.08

0.2

0.1

0.1
3
3

mm/y

Nil
25
.18

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

0.1
10
7

38
48
03
Nil
Nil
Nil
Nil
Nil
10
.05
01

15
19
1
Nil
Nil
Nil
Nil
Nil
4
2
0.4

1.04

20
Nil

Nil

Nil
10
.13

41

8
0.1

0.1

0.1
4
5

3.05
10.92
43
97

Nil

0.3
30
.25

120
430
17
38

0.1

1
12
10

25

01
Nil

Nil

Nil
03
.02

10

05
0.1

0.1

0.1
1
0.9

12.45
86
25
05
Nil

Nil
20
.20

Nil

49
0
34

a Conditions:

1Field
2Field
3Field
4Field
5Field
6Field
7Field

test
test
test
test
test
test
test

in
in
in
in
in
in
in

closed autoclave converting castor oil to drying oil.


top of kettle while refining high purity linseed oil.
receiving tank for dirty palm used in tin-plate line.
distillation column handling crude vegetable oils plus palmitic and stearic acid (acid value of 85-95).
distillation column for cottonseed oil acids.
top of distillation column handling palmitic and stearic acids.
top of distillation column deodorizing crude cottonseed fatty acids by steam distillation.

Page 45

10
2
Nil

0.1
8
8

Nil_

TABLE LIV
Corrosion of Alloys in Animal Fatty Acids
a

Conditions
Temp. C (F)
Time, days
Exposure

1
100 (212)
130
Liquid

2
250 (482)
147
Liquid

3
250 (482)
210
Vapor

4
250 (482)
84
Vapor

Corrosion Rate
Alloy
Mild Steel
Cast Iron
Ni-Resist Type 2
Type 304 Stainless Steel
Type 316 Stainless Steel
INCONEL alloy 600
Nickel 200
MONEL alloy 400
Copper

mm/y
.18
1.63
.23
Nil
Nil
Nil
.08
.05

mpy
7
64
9
Nil
Nil
Nil
3
2

mm/y

.36*
Nil
.01
.41
.58

*Pitted
a Conditions:

1Field
2Field
3Field
4Field

test
test
test
test

mpy

14*
0.1
0.3
16
23

mm/y

mpy

Consumed

Consumed

>3.46
.33
.05*
.01*
.01
.13
.15

>140
13
2*
0.2*
0.3
5
6

mm/y

mpy

Consumed

Consumed

.79
.20
Nil
.05
.08
.10
.13

31
8
Nil
2
3
4
5

References 28,49
in storage tank for mixed acids from fish oils.
in outlet of preheater to distillation column processing animal tatty acids.
in overhead vapor of column distilling acids from fish oils.
on feed tray of distillation column handling crude fatty acids from tallow.

fraction at various temperatures. It is obvious that at some


place above 300 C (572 F) the use of the 300 series
stainless steels is questionable in such a mixture. At this
point, the use of the more highly alloyed materials should
be investigated.
The vegetable oils, characterized by stearic and palmitic
acids among others, appear to have somewhat less aggressive characteristics than the tall oil acids. Table LIII shows
data for the exposure of alloys in a diverse group of field
exposures. It will be noted that INCONEL alloy 600 and
Type 316 stainless steel are resistant to all of the processing
conditions. Indeed, INCONEL alloy 600 vessels have
been used for over 30 years with good success in the
processing of vegetable oil acids. Other aspects of the
handling of these vegetable oil fatty acids would be the
same as described for the tall oil acids.
Those acids derived from animal fats appear to be
somewhat more aggressive. Table LIV shows data obtained while processing acids derived from fish oils and
beef tallow. Again, the INCONEL alloy 600 and Type 316
stainless steel appear to be the most attractive materials
for construction of such equipment.
E. Di and Tricarboxylic Acids
Although the di and tricarboxylic acids are produced in
less quantity than the monobasic acids, the products
constitute a most important industrial commodity. Many
of the acids and corresponding anhydrides are used in the
synthesis of drugs, food products, plasticizers and resins.
Citric, oxalic and certain other of the acids are used
extensively as metal cleaning agents. However, the most
important of the products are maleic and phthalic
anhydrides used to produce alkyd and polyester resins,
the para-phthalic acid used in the preparation of polyester
fibers and adipic acid required for nylon synthesis.

The lower acids of this series are more aggressive in


aqueous solution than are the monobasic acids at the same
temperature and concentration. Dissociation of these
acids in water is greater than for acetic or formic acid. In
addition, the multiple acid grouping has the capacity to
solubilize cations by chelation. Thus, protective, insoluble
corrosion products are normally not found on the surface
of a metal attacked by this group of acids. This allows
continuous attack on the clean metal surface. Since the
rate of attack is not as severe as when using mineral acids,
oxalic, citric and certain other of the dibasic acids are used
to clean metal surfaces.
The elemental dibasic acid is oxalic (ethanedioic) acid;
sublimes at 150 C (302 F). As with other first
homologues of a series, oxalic acid is extremely
aggressive in its attack on most metals. Rates of corrosion
are significantly higher on alloys than with acetic acid at
the same concentration and temperature (Table LV).
However, the relative corrosion resistance of the alloys
remains essentially the same. Higher alloying is required
to provide an alloy with useful resistance to attack. For
instance, Type 304 stainless steel is attacked excessively
in most concentrations of the acid at temperatures above
ambient, and Type 316 stainless steel, although
significantly more resistant, has severe limitations of use.
Table LVI shows the corrosion to be expected by
exposure of a variety of alloys to oxalic acid. More
corrosion data are available for the 10 per cent concentration of the acid at the boiling temperature than far other
combinations, because: (a) 10 percent represents saturation in cold, 25 C (77 F), water, (b) the mixture is an
aggressive cleaning solution for metals and (c) the mixture is often used as a corrosion test medium for the
evaluation of alloys.
It is obvious that higher amounts of nickel in an
austenitic base are beneficial in combatting attack by

Page 46

TABLE LV
Corrosion of Annealed and Heat Treated Alloys
in Dicarboxylic Acids
Laboratory test in 10% boiling dibasic acid stated for 5 days without aeration or deaeration. Acetic
acid added for comparison.
Corrosion Rate
Oxalic
Acid
Alloy

Maleic
Acid

Phthalic
Acid

Acetic
Acid

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

Type 316L Stainless Steel (annealed)

.94

37

.01

0.2

.01

0.2

.01

mpy
0.3

Type 316L Stainless Steel

.66

26

.01

0.2

.01

0.3

Nil

<0.1

CARPENTER alloy 20Cb-3 (annealed)

.58

23

.01

0.2

Nil

<0.1

Nil

<0.1

CARPENTER alloy 20Cb-3

.23

Nil

<0.1

Nil

0.1

Nil

0.1

.51
.38

20
15

Nil
.02

0.1
0.7

Nil
Nil

<0.1
0.1

Nil
.05

<0.1
1.8

(Heat treated)*

(Heat treated)*
INCOLOY alloy 825 (annealed)
INCOLOY alloy 825

(Heat treated)
*650 C (1200 F) for one hour, water-quenched.

steel can be reduced essentially to zero in even boiling 10


per cent acid by the addition of approximately 50 ppm of
35
iron as ferric oxalate.
As noted in Table LV, the dibasic acids above oxalic in
the series are much less corrosive. Maleic acid, m.p. 130 C
(266 F), can be considered as the next homologue, and
the acid is innocuous in aqueous solution when compared to
oxalic acid.

oxalic acid. As with corrosion in the monobasic acids, the


addition of molybdenum is very beneficial. Nickel-base
alloys containing molybdenum exhibit the best resistance
of all alloys in hot, aqueous oxalic acid (Table LVI). Less
costly alloys, such as Type 316 stainless steel, can be used
for specific applications at temperatures somewhat higher
than ambient in aqueous solutions of the acid. Streicher
has shown that the rate of attack on Type 304 stainless

TABLE LVI
Corrosion of Alloys by Oxalic Acid
Laboratory tests without aeration or deaeration except as noted
% Oxalic Acid
Temp. C
F
Test Period (days)

1
Boiling
Boiling
1.5

10
25
77
7

10
35
95
6

10
50
122
6

10
80
176
0.1-10

10
Boiling
Boiling
2-10

30
60
140
11

Corrosion Rate
Alloy
Type 430 stainless steel
Type 304 stainless steel
Type 316 stainless steel
Type 216 stainless steel
ALLEGHENY alloy AL-6X*
Act CN-7M
HASTELLOY alloy C-276
HASTELLOY alloy B
ELGILOY**
Titanium
Vanadium
C71500 (70-30 Cupro-nickel)
WAUKESHA No. 23
WAUKESHA No. 54
WAUKESHA No. 88
KROMARC 55
Multiphase MP35N

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

.81

32

(1)
.03

.03

(1)
1

.03
(2)
.41

1
(2)
4

(1)
.81

11.68
(2)
.25

(1)
32

460
(2)
10

(1)
1.52

(1)
60

63.5
(1)
21614.48
.18 2.44
1.52
.28
.18
.25
.13
.10
24.173.7
(2)
5.46

.63
.48
.05
.23
.10

(1) Type 304L material heat treated at 675 C (1250 F) for 1 hour
(2) Aerated.

*Trademark of Allegheny Ludlum Steel Corporation.


**Trademark of Elgiloy Co.

Page 47

mpy
2500
(1)
85570
796
60
11
7
10
5
4
950
(2)
215

25
19
2
9
4

mm/y

mpy

.20

TABLE LVII
Corrosion of Alloys in Aqueous
Maleic Acid Solutions
Corrosion Rate
2%*
Alloy

mm/y

5%*
mpy

mm/y

10%*

30%**

mpy

mm/y

mpy

40%*

mm/y

mpy

59%**

mm/y

mpy

mm/y

mpy

Type 304 Stainless Steel

.03

.03

4.06

160

4.06

160

3.71

146

5.33

210

Type 316 Stainless Steel


CARPENTER alloy 20

Nil

Nil

Nil

Nil

Nil

Nil

<.03
<.03

<1
<1

Nil

Nil

<.03
<.03

<1
<1

.08

<.03

<1

Nickel 200

.91

36

Copper (C10200)
Silver (fine)

.10

.03
Nil

2
Nil

HASTELLOY
HASTELLOY

alloy C
alloy B

*At 50 C (122 F) for 4 days with agitation by aeration.


**Boiling for 6 days without aeration or deaeration.

Actually, there is little industry interest in maleic acid.


The acid is a contaminant in processes used to produce
maleic anhydride and phthalic anhydride. These
anhydrides are important basic building blocks for the
preparation of polyester and alkyd resins, plasticizers and
agricultural chemicals. The isomer of maleic acid, termed
fumaric acid, has commercial applications in the prepara-

tion of paper sizing and other resinous products as well


as the synthesis of food additives.
The presence of maleic acid in process streams of
the anhydrides does create corrosion problems. The
anhydrides are essentially innocuous, but the presence of
malefic acid at the high temperatures used in the various
processes means attack on lower alloys by streams con-

TABLE LVllI
Field Exposure of Alloys in a Phthalic Anhydride Plant
Corrosion Rate
Exposure

Alloy

10

11

12

13

14

mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy
1
2
1
<0.
1
<0.
1
<0.
1

<0.
1
0.1
0.2
7

.05
.05
.03
.01
.01
.01
Nil
Nil

Nil

.01
Nil
.01
.13

.02

2
2 1.22
1 .56
0.2 .10
0.4 .03
0.2 .03
<0. .03

<0.

<0.

1
.03

.08

0.4 .08
0.1 1.14

0.2
5 .03

39
19
0.3
0.1
<0.
1

<0.
1

33
74
44

39
48
0.7
0.1

<0.
1

0.1
0.8
22
51
22

1.93

Nil
<0.1 .01

Nil
<0.1 .01

Nil

Nil
Nil
<0.1

.01
01
>5.0 0.2 Nil
8 >200 .01
01 0.4 Nil
>5.0 >200 .01
8 160 .01

4.06
< 0.1

Nil

76 >7.62 >300 3.10 122

3.02 119
38

.97
11
0.2

.28

2.21 87
0.2
.99 39 .02 0.6
0.1
.28 11 Nil <0.1

0.1
.86 34

0.2
.51 20

Nil
Nil <0.1

0.3

6
0.1 1.22 48 .15
27
3

.69
5
2
51 20 .13
18

.46

.56
22

Mild Steel
Cast lron (gray)
Ni-Resist Type IV
Type 304 Stainless Steel
Type 309 Stainless Steel
Type 316 Stainless Steel
Type311 Stainless Steel
CARPENTER alloy 20
ACI CN-7M
INCOLOY alloy 825
HASTELLOY alloy C
HASTELLOY alloy B
INCONEL alloy 600
Nickel 200
MONEL alloy 400
Copper
Titanium
Aluminum 3003

.03
.05
.03
Nil
Nil
Nil

Nil
Nil
.05
.18

Mel

*Pitting

FIXED BED NAPHTHALENE OXIDATION UNIT


a1- Mixture of phthalic and malefic anhydride vapors near exit throat of a converter at 200-380C (329-716F) for 71 days. High temperature
excursion to cause melting of 3003 aluminum.
2- Vapors of phthalic and maleic anhydride near bottom of distillation column at 204C (396F) for 16 days.
3- Same column as No. 2, but exposed at top at temperature of 195C (383F).
4- Liquid and vapor of phthalic anhydride in the lights heater at 177C (351F) for 157 days.
5- Overhead of distillation column for phthalic acid dehydration to phthalic anhydride and resulting distillation at 107-143C (225-289F) for
14 days.
6- Near top of batch still column with phthalic and malefic acids present. Distillation Involved 1 :10 ratio of total reflux versus distillation at
100-143C (212-289F) for 95 days.
7- On top tray of phthalic anhydride purification still with small amount of malefic acid and water present at 96-140C (205-284F) for 45
days. Vapor velocity of 7 ft per sec.
8- Top of distillation column for phthalic and maleic acids at 70C (158F) for 22 days.
9- Vapor space of column distilling 7% phthalic acid in water at 180C (356F) for 40 days.
10- Immersed in maleic acid recovery holding tank (10-18% maleic acid plus little phthalic acid and a-naphthoquinine) at 35C (95F) for 27
days.
11- Crude phthalic anhydride vapor in treater tank at 160-285C (320-545F) for 59 days. Liquid and vapor exposures essentially the same.
12- On reflux distributor plate of batch still handling crude phthalic anhydride containing phthalic acid, malefic acid, benzoic acid and maleic
anhydride at 165-260C (329-500F) for 56 days.
13- Same as No. 12, but in another plant using temperatures of 225-290C (437-554F) for 85 days.
14- Same as No. 11, but in plant of No. 12. Essentially same temperatures for 25 days.

48 .01* 0.4*
22 .01 0.3
4 .01 0.2
1
Nil <0.1 .99
1
Nil <0.1 .48
1
Nil <0.1 .01

Nil

Nil

Nil

1
Nil <0.1 .84
3
Nil <0.1 1.88
3
Nil <0.1 1.12
45 .69 27

1 .05*
2

.41

.02

16 .99
1.22
0.6 .02

Nil

Nil

Nil

.02

.56
1.55

.56

Page 48

.56

.01

Nil
Nil

22 5.08 200

3.3 Nil 0.1

Nil .02 0.7


Nil Nil 0.1

Nil

Nil
Nil
.01

Nil

0.1
.18
.20

0.1

<0.1
<0.1
0.2

0.1

0.3
7
8

taining the molten acid or in scrubber waters rich with the


water-soluble acid. As an example, the majority of equipment used in the butane oxidation process for maleic
anhydride was originally of Type 304L stainless steel
construction. However, unforeseen accumulations of maleic acid in portions of the equipment dictated a shift to the
use of the more resistant Type 316L stainless steel. The
benzene process to produce the anhydride is even more
corrosive, and Type 316L stainless steel is used extensively throughout the process chain.
Corrosion to be expected from exposure of alloys in
various aqueous concentrations of maleic acid at the
boiling point is summarized in Table LVIL These data
relate to the corrosion found in process scrubber systems
where water is used as the scrubbing medium. Note the
loss of Type 304 stainless steel as a usable material of
construction at concentrations of 10 per cent or more acid.
Higher iron-base stainless steel alloys, such as Type 316L
and above, show acceptable resistance in all aqueous
concentrations.
The determination of corrosion rates for the stainless
steels in both aqueous and molten maleic acid compositions is difficult. The maleic acid in the absence of more
aggressive anions is slow in penetrating the oxide film on
the stainless steels to initiate corrosion. Consequently,
multiple tests of sufficient duration must be conducted to
provide meaningful rate data for the corrosion process.
Also, during the test period, a conversion of a portion of
the maleic acid to insoluble fumaric acid will occur, which
must be taken into account if the data are to be precise.
Pure maleic acid in the molten form is not encountered
normally in industry, but does exist in certain of the
anhydride process streams. See Table LVIII for field
corrosion data obtained in streams containing the molten
acid as a contaminant.

TABLE LIX
Corrosion of Alloys in
Phthalic Acid and Phthalic Anhydride
Conditions: Laboratory test of duplicate specimens at
150 C (302 F) for 13 days without aeration
ordeaeration.
Corrosion Rate
Phthalic
Anhydride
Alloy

1:1 Phthalic
Anhydride:
Phthalic Acid
Mixture

Phthalic
Acid

mm/y

mpy

mm/y

mpy

mm/y

mpy

<.03

<1

<.03

<1

.03

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

<.03

<1

Mild Steel
Type 304
Stainless Steel
Type 316
Stainless Steel

Phthalic acid, decomp. ca. 200 C (392 F), is found in


many of the same process streams containing the maleic
acid. However, the contribution of phthalic acid to corrosion of the equipment is minimal. Table LIX shows
corrosion data for steel and Types 304 and 316 stainless
steels exposed to hot phthalic acid, phthalic anhydride and
a mixture of the two. These chemicals are not aggressive.
However, the austenitic stainless steels are often used to
process these chemicals to prevent contamination of the
product and to provide a surface that can be cleaned
readily.

TABLE LX
Corrosion of Alloys in Terephthalic Acid Media
Laboratory Test
6% Terephthalic
Acid in Water

Laboratory Test
6% Terephthalic Acid
84.6% Acetic Acid
9.4% Water

Field Test
TPA Leach Feed
Slurry (TPA +
Acetic Acid)

Field Test
Leach Crystallizer
Liquid (14.1 % TPA,
82.7% Acetic Acid,
2.7 % water)

232
450
24

232
450
24

260
500
14

177
351
523

Temperature, C
Temperature, F
Test Period, days

Corrosion Rate
Alloy
Type 304 Stainless Steel
Type 316 Stainless Steel
Type 216 Stainless Steel
Type 317 Stainless Steel
CARPENTER alloy 20Cb-3
INCOLOY alloy 800
HASTELLOY alloy C- 276
Titanium

mm/y
.01
.01

Nil
Nil

mpy
0.4
0.3

0.1
<0.1

mm/y

mpy

mm/y

mpy

mm/y

.06
.02

Nil
Nil

2.4
0.8

0.1
0.1

.19

.04
Nil

7.3

1.5
0.1

.03

.01
.02
.35
.03
Nil

Page 49

mpy

1.0

0.2
0.7
13.8
1.1
<0.1

TABLE LXI
Corrosion of Alloys in Adipic Acid Process
Low temperature, 100 C (212 F), reaction with ammonium vanadate and cupric ion, process involved
oxidation of cyclohexanone and cyclohexanol (KA oil)
in strong nitric acid. In addition to the desired adipic
acid, succinic, glutaric and lighter acids were formed in
the process.
Corrosion Rate
Reactor

Scrubber

Separation
Still

Absorber

mpy mm/y

mpy mm/y

Crystallizer

mpy mm/y

Lower
Acids
Stripper

mpy mm/y

Crystallizer

mpy mm/y

Centrifuge

mpy mm/y

Product
Washing
and
Drying
Equip.

Alloy

mm/y mpy mm/y

Type 304
Stainless Steel
Type 316
Stainless Steel

.23

.30

12

.23

.91

36

.18*

7*

.41

16

.03

.13

mpy mm/y mpy

Nil

Nil

.36

14

.05

.05

.30

12

.08*

3*

.05

.03

.05

Nil

Nil

CARPENTER

.10

.05

.03

.13

Nil

Nil

.03

Nil

Nil

.03

Nil

Nil

HASTELLOY

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

alloy C-276
Titanium

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil*

Nil*

Nil

Nil

Nil

Nil

Nil

Nil

Nil

Nil

alloy 20Cb-3

*Pitting indicated

Data derived from corrosion tests in a large phthalic


anhydride plant are presented in Table LVIII. These show
that, in addition to the higher stainless steels, the use of
Alloys 400, 600 and other nickel-base alloys is permissible
in many areas of the process. For equipment handling the
brominated anhydride, the use of HASTELLOY alloy C276 has proven to be attractive.
Terephthalic acid (para-phthalic acid) is produced in
large quantity, primarily for the preparation of polyester
resins used in the textile industry. A number of processes
have been investigated to produce the acid in as pure form
as economically as possible.
Initially, the process required the oxidation of xylene
using a bromide catalyst. Inasmuch as acetic acid is used as
a dilulent in the process, the reaction mixture of a halogen
and acetic acid was extremely corrosive. HASTELLOY
alloy C-276 was the only contender for use in these areas.
Once the bromide ion was removed, Type 316 stainless
steel was found to be useful for the vast majority of the
remainder of the equipment.

TABLE LXII
Laboratory Tests for Corrosion of Alloys
in Molten Adipic Acid at 170 C (338 F)
Corrosion Rate
Alloy

mm/y

mpy

Type 304 Stainless Steel

1.30

51

Type 321 Stainless Steel

.43

With the research interest to produce a simpler and


more economical mode of preparation, a number of new
methods have evolved. One of the more common procedures is the use of oxygen along with a cobaltic ion
catalyst to effect the reaction. Again, acetic acid is used as
the medium for the reaction. Thus, acetic acid is the
primary corrosive to be considered. Contamination of the
acetic acid by the terephthalic acid (TPA) adds little to the
corrosion produced. The major problem is one of handling an acetic acid medium at high temperatures. There
are a number of steps in the process where the temperatures are well above those required for producing acetic
acid itself. In these areas, the use of materials suitable for
exposure in acetic acid at high temperatures under oxidizing conditions are acceptable. (See discussion of acetic
acid.)
Table LX shows data generated by both laboratory and
field tests designed to explore corrosion within the area of
the leaching step of the process. At this point, the acetic
acid medium is taken to a very high temperature to allow
the rather insoluble TPA to precipitate from solution
before taking the material to a crystallizer. It will be noted
that Type 316 stainless steel is a borderline material for
this specific area because contamination of this stream is
undesirable. Titanium is favored for this most aggressive
area in the process. For all of the remainder of the process,
the use of Type 316 stainless steel has been found to be
most satisfactory. It is necessary to avoid the presence of
crevices or other areas where differential corrosion cells
can be created in either titanium or the Type 316 stainless
steel equipment.

17

Page 50

Adipic acid is an essential ingredient in the production


of nylon resin. The process to produce this dibasic acid is
quite lengthy and corrosive in the latter stages.
Cyclohexane, produced as a hydrogenated benzene, is
oxidized to cyclohexanone and cyclohexanol in a conventional oxidation process. The conditions of this preparation of the KA oil are not exceptionally corrosive, and
steel is used for large portions of the process equipment
with Type 304 stainless steel used where moisture,
organic acids, or other corrosive agents tend to accumulate. The KA oil is then oxidized with strong nitric acid at
approximately 100 C (212 F) to produce adipic acid and
other degradation products from the oxidation step. These
include succinic acid, glutaric acid and all of the lower
monobasic organic acids. The ammonium vanadate and
cupric ion catalyst contributes little to the corrosion
afforded by the strong nitric acid. Inasmuch as problems
relating to this portion of the process are engendered by
the nitric acid, Type 304L stainless steel is used extensively in the equipment. Where dilution occurs or corrosion by the organic acids becomes predominant, Type
316L stainless steel is used. This is particularly true in the
scrubber, absorber and the first centrifuge of the latter
process. The temperatures are maintained as low as
possible by vacuum equipment for economy and to
reduce corrosion throughout the process. Table LXI
shows typical data for common alloys in the latter steps of
the adipic process operation. Note the excellent resistance
of the more highly alloyed stainless steels to conditions
existing through the unit. Care must be exercised in the
choice of Type 304 or Type 316 stainless steels for specific
uses. However, with a judicious choice of material, the
stainless steels can be used extensively throughout the
process.

Pure molten adipic acid is corrosive to an austenitic


stainless steel without molybdenum. Table LXII shows
rates of .43 mm/y or more (17 mils per year or more) in a
molten adipic acid at 170 C (338 F). Type 316 stainless
steel should show adequate resistance to such an exposure.
The higher dibasic acids present unique problems when
appraising the potential for corrosion of the common
alloys. In general, aqueous solutions of the acids are only
mildly corrosive up to 100 C (212 F). For instance, water
saturated wth succinic (butanedioic) acid at 95 C (203 F)
produced no corrosion of Type 304 stainless steel during a
test period of one week.
The molten acids can vary in aggressiveness depending
on the residual contaminants from the process. These
contaminants may be lower organic acids or inorganic
compounds which control to a great extent the rate of
penetration of passive films on the stainless steels and the
subsequent corrosion rate observed. Corrosion data reported for these higher acids seldom if ever identify the
purity of the acid tested.
Table LXIII provides information regarding the corrosion of alloys during the synthesis of a glutaric (pentanedioic) acid-anhydride mixture. The oxidation step,
conducted at relatively low temperatures, was not corrosive to the stainless steels, as would be expected. However, when the reaction mixture was heated to higher
temperatures with the attendant loss of the oxidizing
species, corrosion of the stainless steels became much
more pronounced. The more highly alloyed materials
retained good resistance to the more rigorous conditions
of the high temperature distillation.
Similar data representing the distillation of pimelic

TABLE LXIII
Corrosion of Alloys in Glutaric Acid
Glutaric Anhydride Mixtures
Conditions:
Temperature, C
Temperature, F
Exposure, days

40-90
104-194
1
(oxidation)
7

210
410
1
(distillation)
9

260
500

210
410

13.5

Corrosion Rate
Alloy

mm/y

mpy

mm/y

Type 304 Stainless Steel


Type 316 Stainless Steel
CARPENTER alloy 20

<.03
Nil

03

3.56

<1
Nil

140

1.58
.28
.15
.56
66
<.03
Nil

30

Type 201 Stainless Steel


Type 202 Stainless Steel
HASTELLOY alloy B
HASTELLOY alloy C
INCONEL alloy 600

Copper
MONEL alloy 400

mpy
62
11
6
22
26
<1
Nil

12

mm/y
.94
.20

.86

<.03
Nil

Nil

mpy

mm/y

mpy

37
8

34

<1
Nil

.69
41

23
18
.20

27
16

9
7
8

(1) Pilot unit operations. Acetic acid present in mixture.


(2) Laboratory kettle test designed to represent mixture for field distillation (no acetic acid present); 3 parts acid: 1 part anhydride.
(3) Actual field distillation.

Page 51

F. Naphthenic Acids

TABLE LXIV
Corrosion of Stainless Steels in Molten
Pimelic (Heptanedioic) Acid
Conditions: Metal specimens completely immersed in
molten acid under quiescent conditions at
225 C (437 F). Unreported contaminant
suspected to be present. Results shown
are averages of duplicate tests.
Corrosion Rate
Initial 117 hr
Alloy

Second 73 hr

mm/y

mpy

mm/y

mpy

Type 304 Stainless Steel


Type 347 Stainless Steel

9.36
5.89

369
232

12.89
7.26

508
286

Type 316 Stainless Steel

1.65

65

2.77

109

(heptanediocic) acid are summarized in Table LXIV The


greater corrosive activity of the acid in these tests is
probably attributable to a process contaminant. Although
the higher iron-base and nickel-base alloys were not
tested, it is probable that these alloys would be satisfactorily resistant under such conditions, particularly the
nickel-base molybdenum-chromium-iron alloys.
The tricarboxylic acids without other functional groups
are found in nature (e.g., tricarballylic acid in beets), but
are produced by industry only as a development chemical.
No corrosion data are known to have been published
concerning those compounds. It is possible that such a
structure would generate corrosion comparable to that
observed for citric acid. (See Section G-4, Part III.)

A vacuum distillation column at a major petroleum company. This photo


shows the crossover piping loops in foreground and 1,500 mm (60-inch)
transfer line entering column tangentially. The transfer line and the
column are lined with Type 316 stainless steel to resist naphthenic acid
and sulfidic corrosion.

The naphthenic acids have received much attention during


the past 20 years as a corrosive in process streams of the
oil refineries. A considerable volume of data has been
generated relating to the operation of equipment handling
29, 36-40
streams contaminated with these acids.
The term naphthenic acids describes a group of aromatic compounds containing one or more carboxyl groups
and does not refer to a specific structure. The term embraces acids from benzoic through those of the true naphthenic structure, all of which can contribute to corrosion at
the very high temperatures of oil refining. The corrosive
potential for streams containing these acids is defined by
neutralization number rather than acid content. Thus,
all acidic materials in the stream are categorized by the
term naphthenic acid.
Providing materials of construction to resist naphthenic
acid corrosion is not difficult, although the economics of
selection are critical. When the neutralization number
exceeds 0.5, the streams are considered to be corrosive to
steel. The use of an austenitic stainless steel will provide
resistance to corrosion during processing of the streams.
However, the economics of providing materials of construction for such large process equipment requires that
the optimum material be found. Thus, the various alloy
materials between steel and the 300 series austenitic

Fig 13 Corrosion Isotherms for Various Steels and MONEL alloy 400 in
White Oil/Naphthenic Acid Blends at 235 C (455 F) Temperature

Page 52

stainless steels are explored as potential candidates. The


ease of fabrication of the Type 304 stainless steel, combined with its more than satisfactory corrosion resistance,
makes the material a prime candidate for such service.
No corrosion of Type 304 stainless steel in the most
basic of the aromatic acids (benzoic) is apparent. Tests
using a two per cent aqueous solution at 100 C (212 F) or
of 10 per cent in an anhydrous octanol solution at 130 C
(266 F) produced no attack on the alloy.
In many instances, the corrosion attributable to organic
acids in such systems is compounded by the presence of
sulfur compounds, the lower aliphatic acids, chlorides and
other contaminants. Thus, in making a choice of materials
for such service, the possible effect of chloride ion, sulfur
ions, or other contaminants that may accumulate at times in
the equipment must be considered. Stress-corrosion
cracking of the austenitic stainless steels can be experienced under certain circumstances and must be evaluated
thoroughly before the choice of such an alloy is made.
Gutzeit has pointed out that the corrosion in such
systems is directly related to the neutralization number.
Curves showing the corrosion rate for various alloys as
related to the neutralization number are provided in his
40
paper. One of those is reproduced here as Figure 13.
Corrosion occurs in the liquid phase with only mild
corrosion experienced in the vapor areas. Thus, hot
condensate is always a potential corrosive in such a
system. The use of Alloys 400 or 600 and 800 in such
systems has merit. If stress-corrosion cracking of the
stainless steels are experienced, the use of these alloys
should be considered.
G. Organic Acids with Other
Functional Groups
There are a large number of organic acids of complex
structure which have found extensive use in industry and
home. The corrosion characteristics of this group of
compounds varies widely, as do the organic structures.
Organic acids with other functional groups describe the

normal carboxylic acid terminus to the molecule, and, in


addition, the incorporation of a halogen, an amino, a
hydroxy addition, or other active ion added to the molecule which brings unique characteristics to the product.
1. Glycolic Acid
The simplest of the organic acids in this category is
glycolic (hydroxyacetic) acid. As an acid in aqueous
solution, the material does not appear to be excessively
corrosive at the lower temperatures. For instance, Type
304 stainless steel will show only .003 mm/y (0.1 mpy)
corrosion rate or less in a 6% solution of glycolic acid at
ambient temperature. At 50 C (122 F) during tests of
eight days, both Types 304 and 316 stainless steels
showed no attack in a 50% aqueous solution. Thus, the
acid could not be described as exceedingly corrosive at
conditions normally encountered. However, it has been
found to be corrosive when heated to higher temperatures
when contained in process streams as a contaminant.
Again, the stainless steels resist attack at the high
temperatures, but areas where steel would normally be
acceptable become impractical with contamination of the
streams by glycolic acid. Type 304 stainless steel is then
required.
2. Lactic Acid
Lactic acid (hydroxypropionic acid) is familiar to most
persons as the corrosive agent in milk. To maintain the
purity of the milk, tanks and tank trucks of Types 302 and
304 stainless steels have been constructed for many years
for the handling of this precious commodity.
As indicated by Tables LXV and LXVI, Type 304
stainless steel and its cast counterpart CF-8 is most
satisfactory for the handling of aqueous lactic acid solutions at the lower and intermediate temperatures. At some
point between 2 and 10%, aqueous solutions of lactic acid
begin to attack Type 304 and CF-8 stainless steels excessively. One can then use Type 316 stainless steel and its
cast counterpart CF-8M which shows good resistance
throughout the range of concentrations and temperatures
explored (Table LXV11). Thorough testing of Type 316

TABLE LXV
Corrosion of Alloys in Various Concentrations
of Aqueous Lactic Acid
Conditions:
% Lactic Acid
Temperature, C
Temperature, F
Test Period, days
Other

0.5
100
212
1

1
65
149
1

2
100
212
1

1%

2%

5
26
79
21

45
26
79
14
Aerated;
agitated

10-50
54
129
15
Field Test
in vacuum
evap.

Corrosion Rate
0.5%
Alloy
Type 304 Stainless Steel
INCONEL alloy 600
C71000
(Cupro- nickel 80- 20)
C71500
(Cupro-nickel 70-30)

5%

45%

10-50%

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

.03

Nil

Nil

.03

Nil

0.1

.20

.02

0.9

1.4

57

References 19, 49

Page 53

service in specific applications. It will be noted that some


rates exceeding .25 mm/y (10 mpy) have been obtained
for the Type 316 alloy in lactic acid at boiling temperatures.
At the higher temperatures, it is considered to be good
practice to use an L-grade stainless steel if welding is to be
performed on the alloy. Table LXVI shows appreciable
differences for annealed and sensitized conditions for cast
stainless steels exposed to the acid at elevated temperatures and pressures. This admonition is true for the use of
the stainless steels in all of the organic acids when exposed
at the higher temperatures.

The use of Alloy 400 and the copper-nickel alloys is


dependent on the aeration to be encountered in the acid
stream. Nickel-copper alloy 400 has excellent resistance
to all concentrations of the hot lactic acid solutions in the
absence of air. However, corrosion becomes excessive if
aeration is provided as a condition of the exposure.

TABLE LXVI
High Temperature Exposure of Cast
Stainless Steels in
Aqueous 50% Lactic Acid
(Laboratory tests in autoclaves for 18-22
hours at temperatures shown)
Corrosion Rate
107 C (225 F) 151 C (304 F) 157 C (315 F) 162 C (324 F)
Alloy

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

Nil
Nil
Nil
Nil
2.29

Nil
Nil
Nil
Nil
90

44.20
Nil
2.03

1740
Nil
80

27.94
39.88

1100
1570

.99
1.65

39
65

CF-8
CF-8*
CF-8M
CF-8M*
Copper

*650 C (1202 F) for one hour, water quenched.

Reference 9

4200-Gallon Uniframe Transport Container. One of a fleet of five


Uniframe Type 304 stainless steel transport tanks with 6 of foam inplace insulation being lifted aboard ship at Seattle with a load of milk
for Alaska. These tanks make the long trip by flatbed truck trailer, ship,
and rail flatcar between Seattle and Alaska.

TABLE LXVII
Corrosion of Alloys in Boiling Aqueous Lactic Acid
Solutions During Five-Day Laboratory Tests
Corrosion Rate
Alloy
Type 304

mm/y

mpy

mm/y

.0854.61 32150

mpy

mm/y

mpy

56.64

2230

7.21

284

Stainless Steel
Type 309

3.30

130

<.03.38

<115

.03

.08.33 313

<.03

<1

.03

.18

<.03

<1

.05

.03

.03

.10

.05

.43

17

.38

15

.13.33

513

.15

.15

Stainless Steel
Type 316
Stainless Steel
CARPENTER
alloy 20Cb-3
INCOLOY
alloy 825
HASTELLOY
alloy C-276
HASTELLOY
alloy B
INCONEL
alloy 600
MONEL
alloy 400
Copper

.33

13

.05

.08

Zirconium

Nil

Nil

Nil

Nil

Nil

Nil

Titanium

.03

.03

<.03

<1

Tantalum

Nil

Nil

Nil

Nil

Nil

Nil

<.03

<1

<.03

<1

Columbium

3. Tartaric Acid
Tartaric acid (dihydroxybutanedioic acid) is one of the
more innocuous acids produced in large quantity. As
indicated by Table LXVIII, the product is not aggressive in
aqueous solution up to the boiling point. Any of the
austenitic stainless steels maintain purity in the product and
prevent undesired contamination when storing or
processing the tartaric acid solutions. Higher alloys are not
indicated to be required for such service.
4. Citric Acid
Citric acid (hydroxypropane tricarboxylic acid) is a more
aggressive compound. This tart-tasting constituent of
citrus products can be handled well by the austenitic
stainless steels. Data for many of the other alloys are
shown in Table LXIX. Here it will be noted that Alloy 400
is a candidate for use in many of the food product services.
Others have described the use of MONEL alloy 400 and
14, 41, 42
other nickel-base alloys for such use.
As with the
other organic acids, the presence of air will determine the
rate of corrosion on Alloy 400 in these solutions. Alloy
600 and other alloys of chromium and nickel have good
resistance to the acid and can be used when desired.

References 49, 51

Page 54

Chloride is a commonly encountered contaminant in


citric acid solutions. The effect on the austenitic stainless
steels of this contaminant in 20% aqueous citric acid is
shown in Table LXX. At levels up to 500 ppm of chloride,
no significant general corrosion occurs on stainless steel

with such solutions. However, the presence of chlorides in


combination with an acid create potential problems of
pitting and stress-corrosion cracking particularly in crevices and other stagnant areas in the equipment.

TABLE LXVIII
Corrosion of Metals by Aqueous Tartaric Acid Solutions
Conditions: Laboratory tests without aeration or deaeration except as noted.
Corrosion Rate
%Tartaric Acid
Temperature C (F)
Test Period, days
Other
Alloy

2
26 (79)
21

5
26(79)
21

10
35(95)
6
Aerated

60(140)
6
Aerated

100(212)
6
Aerated

103(217)
2

35(95)
6
Aerated

25
60(140)
6
Aerated

30
100 (212)
6
Aerated

26(79)
11

60(140)
11

50
60(140)
6
Aerated

35(95)
6
Aerated

100(212)
6
Aerated

57
54(129)
10
Field lead.
yacuum
yap.

mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy

Type 304 Stainless Steel


Type 316 Stainless Steel
CARPENTER alloy 20
INCONEL alloy 600
ELGILOY
Titanium
Zirconium
Vanadium
C71000 (80-20 Cupronickel)
C71500 (70-30 Cupronickel)

Nil

Nil
Nil
.01

Nil

Nil
Nil
0.4

.01

Nil
Nil
.04

.4

.1
Nil
1.5

.01

Nil
Nil
.48

Nil

.03
0.2

Nil
0.1

<0.1
19

.02

0.8

.04

1.6

Nil
11

Nil

Nil

Nil
Nil

Nil

Nil
Nil

.01

Nil
Nil

.02

0.1
Nil

Nil

Nil
Nil

0.1

Nil
<0.1

Nil

Nil
Nil

Nil

Nil
Nil

.01

Nil
Nil

0.4

Nil
Nil

.05

.01
Nil

2.1

0.5
Nil

.06

2.4

.03

1.2

.05

1.8

References 19, 46, 50

TABLE LXIX
Corrosion of Metals by Citric Acid
Corrosion Rate
%
Citric
Acid

Temperature

Test
Period

Type 316
Stainless
Steel

INCOLOY

INCONEL

alloy 825

alloy 600

MONEL

Nickel 200

Days

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

78.8
78.8
78.8
60.8
86
140
216
212
150.8
212

61
60-78*

26
26
26
16
30
60
102
100
66
100
Boiling
100
26
60
Boiling
20
100
Boiling
26
90
Boiling
60
42-64

44
7
21
30
7
7
3
6
3
2
45
6
11
11
7
1
6
6
7
2
1
30
37

Nil

Nil

09

53

02
06

3.5

21

0.6
2.4

.01
.06
.16
.02
.12
.13

.10
.11

.22

Nil

.43
.01

65

Boiling

30

.21

8.1

.12

4.8

.79

31

.19

1
2
5

7
10
15
20
25
30

50

58

212
78.8
140
68
212
78.8
194
140
107.6147.2

*Field test in evaporator during concentration of the acid.


References 19, 49, 51

Page 55

mpy

alloy 400

C71500 (70-30
Cupro-nickel)

CARPENTER

Copper

alloy 20Cb-3

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

2
2.2
6.2
.9
4.9
5

4.1
4.2

8.8

.1

16.8
.5

Nil

.03

.07

.04
.19
.21
.53

Nil

.16
.02

Nil

1.1

2.7

1.5
7.4
8.4
2.1

.1

6.2
.9

.06

.02

2.5

.8

.07

2.8

.01

Nil

Nil
.14

.2

.1

Nil
5.5

7.3

.11

4.2

TABLE LXX
Corrosion of Stainless Steels by Citric
Acid Containing Chlorides
Corrosion Rate
Solution

20 wt. per cent Citric Acid

20 wt. per cent Citric Acid

No Chloride

Metal
Type 304
Stainless Steel
Type 316
Stainless Steel

No Chloride

500 ppm Chloride

85 (185)

Temperature, C (F)

500 ppm NaCl


85 (185)

100 (Boiling) (212)

100 (Boiling) (212)

Specimen 1 Specimen 2

Specimen 1 Specimen 2

Specimen 1 Specimen 2

Specimen 1 Specimen 2

<.03

<1

<.03

<1

.10

.08

<.03

<1

<.03

<1

.03

.03

<.03

<1

<.03

<1

Nil

Nil

Nil

Nil

<.03

<1

<.03

<1

<.03

<1

<.03

<1

5. Chloroacetic Acids
The chloroacetic acids are a most important product for
the preparation of drugs, dyes, agricultural chemicals and
as intermediates for the preparation of other organic
compounds. Monochloroacetic acid and dichloroacetic
acid are normally produced simultaneously and separated
as desired. Trichloroacetic acid may be produced by an
additional process step.

Corrosion data for a wide range of alloys exposed to


various monochloroacetic acid solutions are contained in
Table LXXI. It will be noted that Type 316 stainless steel
appears to be attractive in a number of these exposures.
Such an inducement for use of the austenitic stainless
steels should be approached carefully. Pitting and stresscorrosion cracking in such a medium could be disastrous.
A better choice for handling the product in aqueous

TABLE LXXI
Corrosion of Alloys in Monochloroacetic Acid (MCA)
a

Test
Temperature C (F)
Test Period, days

1
25 (77)

2
25 (77)

3
60 (140)

4
18 (64)
28

5
55 (131)
17

6
170 (338)
22

Corrosion Rate
Alloy
MONEL alloy 400

Nickel 200
INCONEL alloy 600
Copper
HASTELLOY alloy B
HASTELLOY alloy C
HASTELLOY alloy D
CARPENTER alloy 20
Type 316 Stainless
Type 317 Stainless
DURICHLOR

Lead
Silver
30% Nickel Cast Iron
NICHROME V*

mm/y
.18
.51

.03
.10
.03

.20

.66

mpy
7
20

1
4
1

26

mm/y
.28
.56

.33

.97

2.03
.94

mpy
11
22

13

38

80
37

a 1Laboratory

mm/y
.18
.18

.51
.94
.79

2.16

2.21

mpy
7
7

20
37
31

85

87

mm/y
.43
.69
.61
.48
.15
<.03

<.03
<.03
<.03
<.03

.05

mpy
17
27
24
19
6
<1

<1
<1
<1
<1

mm/y
.05
.03
.03
.08
.03
<.03

.05
.08
.05
<.03
.33
.03

mpy
2
1
1
3
1
<1

2
3
2
<1
13
1

mm/y mpy
.10
4
.08
3
3.56 140

.18
7
.36
14

.70
28
20.32 800

1.27
50

.53
21
1.50
59

test in 60% monochloroacetic acid liquor from a process containing 1.5% acetyl chloride, 0.5% hydrogen chloride and the
remainder acetic acid. Light agitation.
2Same as No. 1 with high agitation.
3Field test in MCA liquor comparable to that of Test No. 1
4Field test in tank containing 78% MCA in water with moderate aeration
5Field test in same solution as Test No. 3, but with no aeration.
6Field test in refined MCA in storage tank.

*Trademark of Driver-Harris Company

Page 56

solution would be nickel-copper Alloy 400 or the nickelbased molybdenum-chromium-iron alloy. The use of
Alloy 400 is contingent again on the removal of oxidizing
species from the aqueous systems; residual chlorine, air or
other oxidants, can greatly increase the rate of attack.
For the reaction area in chloroacetic acid production
equipment, where chlorine is reacted with acetic acid,
glass-lined steels, TEFLON-lined, or other fluorocarbon
plastic-lined equipment is often used. HASTELLOY alloy
C-276 appears to be acceptable for many of these exposures, but the conventional process utilizes lined equipment for the reaction area. Other metals such as tantalum
or titanium may also be used if available.
Trichloroacetic acid is perhaps even more corrosive than
monochloroacetic acid. Glass-lined equipment, titanium,
HASTELLOY alloy B-2, DURICHLOR and certain other
specific alloys selected after extensive testing may be used
for handling the material at lower temperatures. None of
the chloroacetic acids should be stored or processed in any
quantity without a thorough understanding of the corrosive
nature of these materials and the judicious choice of the
materials of construction for tankage or process
equipment. Although the nickel-based alloys are prime
candidates for use in these solutions once the free chlorine
is removed, all alloys may show evidence of pitting or
crevice corrosion in the halogenated acids, and a thorough
exploration of corrosion resistance of the various alloys in
a specific stream should be conducted.

systems at moderate temperatures.


The decomposition products of such acids at the higher
temperatures can present unique corrosion problems that
should be avoided. This is particularly true when nickel or
copper-containing alloys are used. Discoloration of the
amino acid can occur when using nickel or copper alloys
at temperatures above ambient temperatures.
The austenitic stainless steels are most satisfactory for
handling the amino acids. No problem with their use is
usually anticipated until temperatures above the boiling
point of the aqueous systems are encountered. Some of the
acids not normally encountered, such as cyanuric acid,
can be corrosive in streams and should be identified as a
potential corrodent when choosing materials of construction for applications involving amine solutions.
7. Sulfoacetic Acid
Sulfoacetic acid characterizes one of those organic acids
containing a sulfur atom. The material is not particularly
corrosive once it is prepared and has the general characteristics of acetic acid itself. If the preparation is made by
the addition of a strong sulfuric acid solution to acetic
anhydride, the process conditions are too severe for use of
the austenitic stainless steels. HASTELLOY alloys B-2
and C-276 are apparently acceptable for this step based
upon service experience. Once the product is prepared, the
austenitic stainless steels are almost always excellent for
handling the acid up to 100 C (212 F).

6. Amino Acids
The aminocarboxylic acids are an important group of
chemicals used for the preparation of drugs, agricultural
chemicals and as precursors for numerous other organic
compounds. As a group, the compounds are not excessively corrosive. The basic material glycine (aminoacetic
acid) provides essentially the same corrosive characteristics as acetic acid at the lower temperatures and is less
corrosive than its counterpart at the higher temperatures.
As the molecule is lengthened, the amino acids become
less corrosive, and those above approximately four carbons in length can be considered as inhibitors in aqueous

INCOLOY alloy 825 tanks for the storage of monochloracetic acid resin
solution. This alloy was required to maintain product purity.

Page 57

PART IV. ESTER PREPARATIONS


is continually removed as the process continues. The
residual sulfuric acid concentration continually increases
and can then create very aggressive conditions toward
latter stages of a batch process run.
The kettle used for this process is of major concern. The
heating coils, calandria, or other heating device sustains
the major corrosion in the process. On the tubes of such a
heater, severe pitting, grooving and general attack develop
by concentration of the acid on the hot surface, by the
formation of tars on the metal and, in some instances, by
the accumulation of corrosive salts from the solution. As a
consequence, it is exceptionally difficult to provide definitive data for the corrosion of a specific alloy in the
preparation of these esters. Only empirical data obtained
over a lengthy period of time will provide proper guidance
for the final selection of the material of construction for
the coils, kettle, vapor lines, condensers and a primary
column for the process.
In Table LXXII, field data obtained by the exposure of
numerous alloys in five different ester preparations are
provided. It will be seen here that considerable variation
exists in the data obtained for any one alloy. Because of
the great turbulence existing and the factors enumerated
above, the corrosion of an alloy in the same process
during two different exposures can be greatly different.
Although the data would indicate that Type 304 stain-

A. Acetic Esters
One major use of acetic acid is as a precursor of the various
esters that become important solvents for paints and other
chemical products. In the production of acetic esters, the
acid is combined with other organic compounds containing a hydroxyl group. The more common esters are ethyl
acetate, butyl acetate, isopropyl acetate and Cellosolve
acetate.
Corrosion to be expected in the preparation of these
esters can vary greatly depending on the operation. If
acetic acid were the only corrosive contaminant present,
the data provided previously for acetic acid could be used
as a guide. Unfortunately, a catalyst is necessary to
improve the efficiency of the process, and in most
instances, the presence of this catalyst determines the
corrosion to be expected. Temperatures required for the
production of these esters will range from 60 to 150 C
(140-302 F), depending on the boiling point of the ester.
Sulfuric acid has long been used as the catalyst for
synthesis of the esters. This is added as concentrated
sulfuric acid in small quantities of only 0.5 to 2.0% of the
total charge. In anhydrous medium, this would not be
excessively corrosive. However, water is produced by the
reaction between the alcohol and acid which can serve as a
temporary diluent for the sulfuric acid. The water formed

TABLE LXXII
Corrosion of Alloys in Batch Acetic Ester Preparations
Conditions: Exposure of racks in same kettle during the preparation of esters
using sulfuric acid catalyst. Temperature varies with ester prepared.
Cupric ion present. Liquid (L) and vapor (V) exposures.
Test 1Ethyl and isopropyl acetate alternately for 50 days @ 110 C (230 F).
Test 2Isopropyl acetate for 14 days @ 110 C (230 F).
Test 3Amyl acetate for 11 days @ 115 C (239 F).
Test 4Ethyl and isopropyl acetate alternately for 81 days @ 110 C (230 F).
Test 5Butyl and methyl Cellosolve acetate alternately for 29 days @ 115 C(239 F) and 150 C (302 F).
Corrosion Rate
1

L
Alloy

mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy mm/y mpy

Type 304
Stainless Steel

.05

.56

22

.15

.28

11

.05

.43

17

.05

.30

12

Type 329
Stainless Steel
Type 316
Stainless Steel
Type 216
Stainless Steel
CARPENTER
alloy 20 Cb-3
JESSOP
alloy JS-700
HASTELLOY
alloy G

<.03

<1

.15

.28

11

.03

.03

.18

.10

<.03

<1

.23

.18

.23

.08

.10

.03

<.03

<1

.23

.41

16

.23

.08

.13

.13

.03

.03

.03

.03

.08

.08

.05

.05

.86

34

.15

.13

.08

.03

1.65

65

.10

4.57

180

.05

1.42

56

.08

2.72

107

.43

17

.13

.03

MONEL
alloy 400
Copper

Page 58

less steel would be satisfactory for immersion conditions


in an esterification kettle, this is most unlikely. The use of
Types 316 or 316L stainless steels is borderline for these
applications. As the alloy content is increased, reduced
rates of attack are obtained, but the economics of the
selection require detailed analysis before committing one
to a final decision.
It will be noted that those materials high in nickel have
good promise for use in the process. It has been reported
that nickel-copper Alloy 400 has been used extensively for
pumps, reactors, heating coils, piping and agitators for
such acetic acid services in unaerated solutions where
22
sulfuric acid is present. The data and literature show that
in numerous instances nickel-chromium Alloy 600 has
exhibited excellent resistance to esterification environments. For instance, INCONEL alloy 600 exposed in an
amyl acetate preparation at 149 C (300 F) during a 28day exposure showed corrosion of only .15 mm/y (6 mpy)
while MONEL alloy 400 showed a rate of .69 mm/y (27
mpy). Some combinations of Type 316 stainless steel,
Alloys 400 and 600 and the copper alloys are indicated to
be the basic choices for this service.
When using an austenitic stainless steel, such as the
Type 316L, it can be shown that a considerable reduction
of the corrosion rate can be achieved by the addition of
oxidizing ions to the solution. Cupric and ferric ions are
both effective for this purpose. One way of providing such
an environment is the use of a copper alloy kettle with
stainless steel heating coils. The stainless steel can have an
adequate life in such service, whereas an all Type 316L
stainless steel system would not be acceptable.
The effect of the concentration of sulfuric acid in such a
batch process can be noted by reference to Table LXXIII.
At the temperatures of the esterification reaction, the
corrosion rate of Types 316 and 316L stainless steels

increases rapidly as the sulfuric acid is concentrated in the


kettle. Also, there can be some small amount of degradation of the acid to provide corrosive sulfur compounds in
the vapor.
The severe effect of the acid conditions on a heating
surface is apparent by reviewing the data of Table LXXIV.
Laboratory hot wall tests of various alloys show the
corrosion to be much higher for the materials than would
be experienced in a simple boiling solution. Certainly,
experience in the field has confirmed the severe corrosion
to be expected on such heating surfaces in the process. For
this reason, graphite calandrias are sometimes used to
assure adequate resistance of the heating element.
There are other, less corrosive acids available for catalyzing the esterification reaction. Toluene sulfonic acid
(TSA) has often been used for this purpose and, in

TABLE LXXIII
Effect of Sulfuric Acid Concentration on Corrosion of
Type 316 Stainless Steel in an Esterification Reaction
Conditions: Solution of 25% acetic acid, 59% butyl
acetate, 10% water and 6% butanol prepared
and sulfuric acid added as indicated. Tests
conducted at the boiling point.
Corrosion Rate

% Sulfuric Acid
Added (as 95% H2SO4)

mm/y

mpy

0.0
0.1
0.5

Nil
.48
5.92

Nil
19
233

1.0

17.53

690

TABLE LXXIV
Hot Wall Tests of Alloys in a Synthetic
Esterification Mixture
Conditions: Laboratory tests using hot wall apparatus for three days (<3 days for alloys showing
high corrosion rates) in a mixture of 83% acetic acid9.3% formic acid3.8% H2S04
3.9% water. Comparison with conventional immersion test at boiling temperature 112 C
(234 F) provided.
Hot Wall
Solution
Temperature
Alloy
E-BRITS 26-1
HASTELLOY alloy G
HASTELLOY alloy C-276
MONEL alloy 400

Copper (C10200)
Zirconium
Type 316 Stainless Steel

Hot Wall
Specimen
Temperature

Hot Wall
Corrosion
Rate

Immersion
Test Corrosion
Rate

mm/y

mpy

mm/y

mpy

120
112
118
118
118
118

248
234
244
244
244
244

150
155
140
137
135
142

302
311
284
277
275
288

3.94
.99
.48
.41
1.42
.03

155
39
19
16
56
1

1.88
.20

3.63

74
8

143

Page 59

general, affords less corrosion of austenitic stainless steel


surfaces than does the sulfuric acid. Table LXXV shows
data obtained by field exposure of various alloys in a TSA
catalyzed reaction during two different runs. Other materials that can be used are benzene sulfonic acid and
acetylsulfoacetic acid (ASA). Of these, the ASA is the
least corrosive to the austenitic stainless steels but increases the rate of attack on copper alloys significantly.
Tables IV and XXI show other data relating to the
preparation of these esters. Table XXI particularly lists a
wide range of alloys evaluated in a synthetic butyl acetate
reaction mixture.
One of the newer catalysts for use under certain
circumstances for esterification reactions is boron trifluoride. Table LXXVI shows data generated by conditions required for such a reaction. Type 316 or Type 316L
stainless steels appear to be adequate for this reaction.
However, extensive testing should be conducted before
committing an austenitic stainless steel to such a fluoride
environment.
As indicated, essentially all the corrosion to be experienced in the esterification process occurs in the reaction
kettle and appurtenant equipment. Distillation of the
esters from the kettle is normally conducted in a Type
316L stainless steel still to assure low corrosion rates in
this equipment. However, further refining of the ester, or
other techniques required for improving the quality of the
product, can be conducted in Type 304 stainless steel

TABLE LXXV

equipment. The ester itself is innocuous and can be


processed or handled in steel equipment if contamination
of the product is not objectionable. Thus, the concern
with corrosion in such a process is centered totally in the
reaction area of the equipment.
B. Phthalate Esters
The phthalate esters are prepared directly from the anhydride in a manner analogous to the preparation of the
acetic esters. The temperatures are higher, but a drier
medium is maintained than during acetic ester preparations. Table LXXVII shows typical data generated by
three exposures of numerous alloys in phthalic ester
preparations. The same general statements as provided
for the acetic esters relate to this type of exposure.
Phthalate esters prepared from octyl, decyl and other
alcohols are important as plasticizers for various plastics.
They also have excellent heat stability and can be used
for heating mediums for a number of processes.
C. Esterification of Fatty Acids
Esterification of the fatty acids to produce soap is not
28, 32-34
Data shown in Table
exceptionally corrosive.
LXXVIII reveal moderate corrosion of the stainless
steels, and very low corrosion rates of the more highly
alloyed materials in three different field exposures. As
with other esterifications, once the esterification itself is
completed, processing of the product becomes much less
difficult; Type 304 stainless steel is satisfactory for such a
purpose.

Corrosion of Alloys in a Typical


Acetic Esters Reaction
Conditions: Batch reactions producing butyl acetate
with kettle exposure of alloys in 25-45%
acetic acid, 30% acetates, 20% alcohol,
5-8% water and 0.75% toluene sulfonic
acid. Test 1 conducted at 107 C (225 F) for
34 days and Test 2 at 121 C (250 F) for 29
days.

D. Acrylate Esters
The acrylate esters comprise one of the newer, more
reactive group of chemicals available for the synthesis of a

TABLE LXXVI
Comparison of Esterification Catalysts on
Corrosion of Alloys

Corrosion Rate
Test 1

Test 2

Alloy

mm/y

mpy

Type 304 Stainless Steel


Type 329 Stainless Steel

11.18
.25

440
10

8.38

330

Type 316 Stainless Steel

.33

13

1.14

45

Type 317 Stainless Steel

.43

17

.36
1.27
.58

14
50
23

HASTELLOY alloy C

.20

HASTELLOY alloy B

.58
.23

23
9

Nickel 200

.51
.99

20
39

.18
.43

7
17

Copper

.51

20

.18

CARPENTER alloy 20
INCOLOY alloy 825
ILLIUM alloy G

INCONEL alloy 600


MONEL alloy 400

mm/y

mpy

Conditions: Preparation of a higher acetic ester in semiworks equipment using 1.5 per cent sulfuric
acid at 75-110 C (167-230 F) during 32
days for Test 1 and 0.32 per cent boron
trifluoride at 75-85 C (167-185 F) for 5
days in Test 2.
Corrosion Rate
Test 1
Alloy
Type 304 Stainless Steel
Type 316 Stainless Steel
E-BRITE 26-1

mm/y
.03
.03
.05

CARPENTER alloy 20Cb-3


HASTELLOY alloy C-276

Copper (C10200)

Page 60

Test 2

mpy
1
1
2

mm/y
.43
.05
2.49

mpy
17
2
98

.03

.03

Nil
.18

Nil
7

Nil
.30

Nil
12

wide range of resinous products. The esters are best


known as the starting material for the preparation of latex
paints.
Previous comments given in the sections on acrylic acid
and the acetic esters are pertinent to the production of the
acrylates. It was pointed out in the discussion of the
acrylic acid that a simultaneous production of the ester
can be achieved starting with propylene. If the process
produces only acrylic acid, the acid is reacted in a manner
27
analogous to that used for the acetic esters.
Ethyl acrylate is produced in a continuous system by
the addition of sulfuric acid, or a similar catalyst, to the
acid in alcohol. As in the case of the acetic esters, the
conditions in the reactor are most aggressive. Type 316L
stainless steel can usually be used for all equipment
following the reaction step, and Type 304 stainless steel
can be used for many of the recovery areas. On the other
hand, the conditions in the kettle can be so severe that
alloy materials higher than the austenitic stainless steels
are required.
Table LXXIX shows typical data from the exposure of
coupons in an ethyl acrylate synthesis. Note the extreme
corrosion of Type 316 stainless steel which occurred. As
in the case of acetic esters, combinations of nickel-copper
Alloy 400, nickel-chromium Alloy 600, copper alloys and
the nickel-base molybdenum-chromium-iron alloys may

be used to reduce corrosion in the reaction area. In the data


shown, conditions in the vapor line from the reactor are
even more corrosive than those encountered in the kettle
liquid. This situation may or may not occur in a similar
unit, depending on the mode of operation.
The coils, or other heating apparatus used on the kettle,
will again experience the greatest corrosion. For this
reason, a major effort should be made to identify the
optimum material of construction for this service. Graphite construction is sometimes used for this specific area.
As for the other ester preparations, Type 304 stainless
steel is adequate for many of the recovery stages following
the reaction. If wash waters are used in the process, the
possibility of stress-corrosion cracking from chlorides in
the water should be considered. Otherwise, the stainless
steels will provide product of a good quality at a minimum
cost. Duplex structured stainless steel such as Type 329 or
alloys containing higher nickel contents such as Alloys
600 and 800 are resistant to chloride stress-corrosion
cracking in this service.
The higher acrylate esters (four carbon and higher) are
produced in a manner comparable to the ethyl acrylate
process. However, the temperatures are higher and the
attendant corrosion is increased. Here the reaction conditions are extremely severe, as noted in Table LXXX.
Extensive corrosion testing should be conducted to identify the desired materials of construction for the reactor

TABLE LXXVII
Corrosion Generated in Phthalic Anhydride Esterifications
Exposure 1Octyl phthalate batch preparation using 0.15% H2SO4 with trace chloride
present in some batches. Exposure of 83 days on 84 rpm agitator shaft in
kettle liquid at average of 149 C (300 F).
Exposure 2Higher alcohols and phthalic anhydride plus 0.5% toluene sulfonic acid
and 0.25% H2SO4 at 140 C (284 F) average for 135 days in kettle liquid.
Exposure 3Toluene sulfonic acid catalyzed reaction of phthalic anhydride and higher
alcohols at 174 C (345 F) for 10 days in glass laboratory kettle.
Corrosion Rate
1
Alloy
Type 304 Stainless Steel
Type 202 Stainless Steel
Type 316 Stainless Steel
Type 317 Stainless Steel
CARPENTER alloy 20
ACI CN-7M Casting
HASTELLOY alloy C
HASTELLLOY alloy B
INCOLOY alloy 825
INCONEL alloy 600
MONEL alloy 400
Nickel 200
Ni-Resist Type2
Copper
Titanium

mm/y

mpy

mm/y

mpy

mm/y

mpy

.25
.30
.15
.08
.03
<.03
.03*
.08*
.03
.10

.18

.08*

10
12
6
3
1
<1
1*
3*
1
4

3*

>1.27

1.60
1.04
.03

<.03
.03
.33
.08
.20
.15

>50

63
41
1

<1
1
13
3
8
6

.05

.05

.03

.13

.18

*No Pitting. All other alloys pitted to some extent.

Page 61

interest from a corrosion standpoint. The Reppe process


prepares the ester from acetylene, carbon monoxide and
alcohol. This reaction is conducted in an acid medium
with nickel chloride present. As a consequence, corrosion
in the reaction area can be very high.
Table LXXXI shows data obtained in a reaction to
prepare ethyl acrylate by this procedure. Note that the
liquid contains over two per cent hydrochloric acid along
with free acrylic acid. Among the alloys tested, only
HASTELLOY alloys B and C-276 appear to offer good
corrosion resistance in this environment. Once the ester is
removed from the reaction medium, the conventional
materials of construction for recovery of the ester can be
employed.

and accompanying equipment. In general, the vapor from


the reactor is no worse than that described for the ethyl
acrylate process. However, the first distillation column in
the recovery chain can experience severe corrosion in the
base, and the use of nickel-base molybdenum-chromiumiron alloys and other highly corrosion-resistant materials
should be evaluated for use in this area.
As described before, conditions in the recovery system
are not severe. The austenitic stainless steels are used for
the vast majority of the equipment. Again, adequate
attention should be given to the possible detrimental
introduction of chlorides or other foreign species into the
streams.
One other method of preparing ethyl acrylate is of

TABLE LXXVIII
Field Exposure of Alloys in
Fatty Acid Esterifications
Exposure 1On agitator shaft in liquid of kettle during esterification of C12-C18 fatty acids with
alcohols + 0.25% H2SO4 at 100 C (212 F) for 33 days.
Exposure 2In liquid of kettle near head during esterification of fatty acids (myristic present) with
alcohols (isopropanol present) with sulfuric acid at approximately 110 C (230 F) for 82
days.
Exposure 3Liquid and vapor phase of a kettle (liquid velocity ca. 16 ft/sec) for 18 days during
glyceryl esterification, amidation and sulfurization of tall oil.
Corrosion Rate
1

Alloy
Type 304 Stainless Steel
Type 216 Stainless Steel
Type 316 Stainless Steel
Type 317Stainless Steel
CARPENTER alloy 20Cb-3
ACI CN-7M Cast Alloy
NITRONIC** 50
INCOLOY alloy 825
INCONEL alloy 600
INCONEL alloy 625
HASTELLOY alloy G
HASTELLOY alloy C-276
HASTELLOY alloy B
JESSOP JS-700
MONEL alloy 400
Nickel 200
Copper
Titanium
30% Nickel Cast Iron
Ni-Resist Type 1

Liquid

Liquid

3*
Liquid

Vapor

mm/y

mpy

mm/y

mpy

mm/y

mpy

mm/y

mpy

.51

.51

.10

.25

.10

.15

20

20

10

.16
.03
.15
.08
.01

.02
.01

.02
.01
.01
.09
.05

.01

6.2
1.1
5.8
3.1
0.4

0.9
0.4

0.7
0.4
0.5
3.7
2.0

_
0.3

.23

.05

<.03

.13

<.03
.18

.56
.97

.33
.15

<1

<1
7

22
38

13
6

<.03

<.03

<.03

<.03

<.03
.15

.30
.36

.15
.30

<1

<1

<1

<1

<1
6

12
14

16
12

*Reference 30
**Trademark of Armco Steel Corporation

Page 62

TABLE LXXIX

TABLE LXXXI

Corrosion of Alloys in Ethyl Acrylate Synthesis

Corrosion of Alloys in Ethyl Acrylate Preparation from


Acetylene

Conditions: Specimens exposed in an ethyl acrylate


reactor for 74 days at a temperature of
110 C (230 F) with sulfuric acid catalyst.
Corrosion Rate
Vapor Line
from Reactor

Base of Reactor
Alloy

mm/y

mpy

mm/y

mpy

Type 304 Stainless Steel


Type 316 Stainless Steel
CARPENTER alloy 20
HASTELLOY alloy G
HASTELLOY alloy C
HASTELLOY alloy B
HASTELLOY alloy D
INCONEL alloy 600
MONEL alloy 400
Nickel 200
Copper
Titanium
Zirconium

.89
.25
.13
.13
.08
.03
.05
.08
.03

.03
.53
<.03

35
10
5
5
3
1
2
3
1

1
21
<1

5.08
>10.16
.33

.20
.51

.91
.58
.63
1.14

200
>400
13

8
20

36
23
25
45

Conditions: Specimens exposed in the reaction kettle


where acetylene, carbon monoxide, ethanol
and nickel chloride were agitated heavily for
17 days. Acids formed were approximately
5% acrylic and 2.5% hydrochloric acid.

Corrosion Rate
Alloy

mm/y

mpy

Type 316 Stainless Steel


CARPENTER alloy 20
HASTELLOY alloy C-276
HASTELLOY alloy B
Nickel 200
MONEL alloy 400
Copper

1.27
.33
.08
.05
.25
2.03
3.30

50
13
3
2
10
80
130

TABLE LXXX
Corrosion of Alloys in Higher Acrylate Esters Production
Conditions: Exposure in base of reactor processing higher
acrylates at 110-160 C (230-320 F) for times
shown. Sulfuric acid catalyst used.
Butyl
67 days

Octyl
11 days

Decyl
11 days

Corrosion Rate
Alloy
Type 316 Stainless Steel
CARPENTER alloy 20
INCOLOY alloy 825
HASTELLOY alloy G
HASTELLOY alloy C
HASTELLOY alloy B
HASTELLOY alloy D
INCONEL alloy 600
MONEL alloy 400
DURIRON

Titanium
Zirconium

mm/y

mpy

mm/y

mpy

mm/y

mpy

3.63-5.49
.13-.58
.61
.10
.08-.61
.15-.28
.08
.66-1.24
.18-.25
.03
.08-.13
.03-.05

143-216
5-23
24
4
3-24
6-11
3
26-49
7-10
1
3- 5
1- 2

10.16
1.78

1.02

2.79

400
70

40

110

>38.1
1.27

.76

1.90

<.03

>1500
50

30

75

<1

Page 63

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Page 64

TRADEMARKS
ALLEGHENY
ALOYCO
AMBRALOY
CARPENTER
CHLORIMET
CROLOY
CRUCIBLE
DURALOY
DURICHLOR
DURIMET
DURIRON
E-BRITE
ELGILOY
EVERDUR
HASTELLOY
HAYNES
ILLIUM
INCOLOY
INCONEL
JESSOP
KROMARC
MONEL
MULTIMET
MP35N
NICHROME
NITRONIC
STELLITE
TEFLON
WAUKESHA
WORTHITE
PH 15-7Mo
17-7PH
17-4PH

PRODUCT OF
Allegheny Ludlum Steel Corporation
Aloyco Inc.
Anaconda American Brass Co.
Carpenter Technology Corporation
The Duriron Company, Inc.
Babcock & Wilcox Co.
Colt Industries Inc.
The Duraloy Co.
The Duriron Company, Inc.
The Duriron Company, Inc.
The Duriron Company, Inc.
Allegheny Ludlum Steel Corporation
Elgiloy Co.
Anaconda American Brass Co.
Cabot Corporation
Cabot Corporation
Stainless Foundry & Engineering, Inc.
INCO family of companies
INCO family of companies
Jessup Steel Company
Westinghouse Electric Corporation
INCO family of companies
Cabot Corporation
Standard Pressed Steel Co.
Driver-Harris Company
Armco Steel Corporation
Cabot Corporation
E. I. duPont de Nemours & Co.
Waukesha Foundry Company
Worthington Corporation
Armco Steel Corporation
Armco Steel Corporation
Armco Steel Corporation